CN1311113C - Spontaneously degradable fibers and goods made thereof - Google Patents

Abstract

A spontaneously degradable fiber excellent in bulkiness, softness, stretchability and feeling, which comprises (A) a low heat-shrinkable fiber component comprising a high crystalline aliphatic polyester and (B) a high heat-shrinkable fiber component comprising an aliphatic polyester, e.g., a low crystalline or non-crystalline aliphatic polyester, and a block copolymer or a mixture the main component of which is an aliphatic polyester and which comprises a high-melting component and a low-melting component. Further, fibers excellent in self-crimpability or self-adhesion property and dividable fibers are obtained by suitably combining the fiber components (A) and (B) to form conjugated fibers or composite yarns.

Description

Natural decomposition fiber and goods thereof

The application is dividing an application of No. 97194524.1, Chinese patent application of the same name, original bill international application no PCT/JP97/01588, international filing date on May 12nd, 1997.

Technical field

The present invention relates to a kind of fiber and goods thereof of natural decomposition, this fiber can provide the fibre of good characteristics such as having bulkiness, flexibility, feel, in more detail, relate to a kind of natural decomposition fiber and goods of making by the different aliphatic polyester of thermal characteristics thereof.

Background technology

Past is slow at the decomposition rate under the natural environment by the synthetic fiber that synthetic resin is spun into, and the thermal discharge when burning is big, therefore, is necessary to re-recognize from the viewpoint of conservation of natural environment.Therefore, developing natural decomposition fiber at present, wishing environmental protection is contributed by the aliphatic polyester spinning.But these aliphatic polyester series natural decomposition fibers exist so not gratifying place at aspects such as bulkiness, flexibility, feels, wish to improve.

In the past, people know, if the fiber combinations that shrinkage is different then can obtain the good goods such as braided fabric of bulkiness and flexibility in compound (mixing) body between common fiber.But, for aliphatic poly ester fiber, almost also do not understand the inotropic method of control, moreover do not know the fiber composite that shrinkage is different fully together, or improve the quality of fabric or volume thing with it with natural decomposition.

In addition, in order to obtain to have the height flexibility or have, since the past, just the composite fibre of Splittable had been cut apart by fiber based on special cross-section form or the various functions that bigger serface produced.Adopt the good braided fabric of flexibility that this method develops and be widely used and gloss, nonwoven fabric, artificial leather, artificial imitative chamois leather, high-performance cloth for wiping or dusting, high-performance filter cloth etc.But, Splittable conjugate fiber is not proposed in the fiber art of decomposing under natural environment as yet.This is combination and dividing method because of the spinning material (polymer) of also not knowing to be suitable for cutting apart.

Make a part of fibers melt, make mutual bonding bonding voluntarily (thermal welding) fiber between the fiber through heating, be widely used in the synthetic fiber field.The thermal welding fiber that uses aliphatic polyester is disclosed in the flat 6-207324 communique of Te Kaiping 6-207320 and Te Kai.But, only disclose in the embodiment with fusing point be 102 ℃ polyethylene glycol succinate as epidermis (bonding composition), the poly butylene succinate that with fusing point is 118 ℃ is as the composite fibre of core silk (intensity maintenance composition), its bonding force is not strong.The fusing point of two kinds of compositions only differs 16 ℃, and is very little, and intensity keeps composition being used for carrying out taking place in the bonding heating process softening and deterioration.In addition, the temperature that this fiber is suitable for adhesion process is limited in the extremely narrow scope, and it is quite difficult wanting to bring into play good bonding force and intensity, and further according to application target, it also is extremely difficult changing bonding strength in wide region, and purposes is restricted.Usually, the bonding composition in the thermal welding fiber uses the low melting point composition.But, if use the low melting point aliphatic polyester of fusing point below 120 ℃, then glass transition temperature is below normal temperature, very low, setting rate is slow, therefore, fiber mutual easily bond (deadlocked) during melt spinning, not only be difficult to make at a high speed, heat resistance is also very low during use, exists many problems in practicality.

The objective of the invention is to, provide all good natural decomposition fiber of a kind of bulkiness, flexibility, feel and retractility and with its woven fibre.

Another object of the present invention is, a kind of natural decomposition fiber of crimpiness voluntarily that has is provided.

Another object of the present invention is, a kind of fiber of crimpiness voluntarily is provided, and this fiber is a natural decomposition, can adopt good the curling of means generation such as heating, all good goods such as flexibility, bulkiness, retractility can be provided, and can be easy to the high efficiency manufacturing.

Another object of the present invention is, a kind of composite fibre is provided, and this fiber is a natural decomposition, has the severability that has improved, and can make fiber or fiber structure with good flexibility and bigger serface.

Another object of the present invention is, the fiber structure that a kind of fiber of caking property voluntarily is provided and uses it, this voluntarily the caking property fiber be natural decomposition, and when employing is used for bonding heat treated and brings into play excellent adhesion, intensity keeps the deterioration of composition few, have good intensity, can also carry out melt spinning at a high speed, and can easily make the bonded fiber structure of excellent heat resistance.

Another object of the present invention is, a kind of fiber of caking property voluntarily is provided, and this fiber is a natural decomposition, can carry out adhesion process in wide temperature range, can change bonding force in wide region according to application target.

The present invention also aims to, a kind of fiber assembly is provided, and this aggregate is a natural decomposition, will mix because of heating waits the different plurality of fibers of shrinkage that produces, make by heating to produce difference in length between the fiber, good goods such as bulkiness, flexibility, feel can be provided.

Summary of the invention

Present inventors further investigate repeatedly, and it found that the caloric receptivity during with fusion (melting caloric) is combined with different natural decomposition aliphatic polyesters of thermal characteristics such as fusing points, can achieve the above object, thereby finish the present invention.

The invention provides a kind of fiber, be to make by (A) with (B), wherein (A) is by fusing point more than 100 ℃ and the fusion fibre composition that the aliphatic poly ester polymer of (following writing J/g) constitutes that recepts the caloric more than 30 joule/gram, (B) be by fusing point more than 100 ℃ and the fusion caloric receptivity lack the fibre composition of the aliphatic poly ester polymer formation more than the 5J/g than the caloric receptivity of this polymer (A).Among the present invention, by fibre composition (A) and the fiber that (B) constitutes, can be the composite fibre form that makes composition (A) and (B) be compounded to form in filament, also can be to make each composition fiber mix the compound silk form that forms.Because this fiber is by the big high crystalline composition (A) of melting caloric low-crystalline composition (B) formation little with melting caloric, therefore, have good bulkiness, flexibility and feel according to the heat-shrinkable difference, particularly formed composite fibre has been given play to good crimpiness voluntarily, and the retractility fiber with excellent can be provided.

The present invention also provides a kind of fiber, make by (A) with (B), wherein (A) is the fibre composition that is made of the crystallinity aliphatic poly ester polymer of fusing point more than 140 ℃, (B) be that the composition (H) that is made of the crystallinity aliphatic polyester of fusing point more than 110 ℃ and fusing point are below 120 ℃ and than low crystallinity aliphatic polyester or the fibre composition that combines of the composition (S) that constitutes at the amorphism aliphatic polyester below 30 ℃ of glass transition temperature more than 10 ℃ of the fusing point of above-mentioned polymer (A).Aliphatic polyester composition (H) in the fibre composition of this fiber (B) and (S) can be the block copolymer form that two kinds of compositions combine, and also can be two kinds of mixture of ingredients forms.This fiber is owing to comprise the fibre composition (A) that is made of the little high-melting-point polymer of heat-shrinkable and contain the low melting point that helps heat-shrinkable or the fibre composition (B) of amorphism composition (S) therefore have good bulkiness, flexibility and feel.Especially, make fusing point more than 140 ℃, the crystallinity aliphatic poly ester polymer (A) that melting caloric 20J/g is above, with differ at least 2 kinds of crystallinity aliphatic polyester compositions (H) more than 20 ℃ and the block copolymer that (S) constitutes and/or mixture (B) the eccentric composite fibre that forms that engages in filament by fusing point, has good crimpiness voluntarily, and this composition (B) is formed and the composite fibre of joint formation on fiber at least a portion surface, has good caking property voluntarily, wherein, said (B) contains fusing point more than 130 ℃, high-melting-point composition (H) 90～10 weight % that melting caloric 3J/g is above, and to contain fusing point be 40～120 ℃, low melting point composition (S) 10～90 weight % that melting caloric 3J/g is above.Further, make composition (A) and at least one side (B) contain the above organopolysiloxane of 0.05 weight %, make the crystallinity aliphatic poly ester polymer (A) of fusing point more than 140 ℃ with, contain crystallinity aliphatic polyester composition (H) and fusing point 120 ℃ below, the glass transition temperature of fusing point more than 140 ℃ and in filament, be bonded into alienable shape, can obtain labile natural decomposition composite fibre thus at the block copolymer and/or the mixture (B) of the aliphatic polyester composition (S) below 30 ℃.In addition, fibre composition (B) is under the occasion of block copolymer, and the crystallinity aliphatic polyester composition (H) of fusing point more than 110 ℃ can contain urethane bond.

In addition, the invention provides a kind of composite fibre, this composite fibre is the crystalline polymer (A) that makes the aliphatic polyester of fusing point more than 140 ℃, the composition (B) that forms with at least a following compound by aliphatic polyester and 1～50 weight % is composited in filament, and in cross section, composition (B) is separated at least 2 parts with polymer (A); Wherein, described compound be selected from polyethers, this polyethers of alkylidene with carbon number 2～4 derivative, have sulfonic organic compound, have sulfate group organic compound, have carboxyl organic compound, have phosphate organic compound, have the organic compound of amino and/or amide groups.This composite fibre because composition (B) contains specific hydrophilic compounds, easily is hydrolyzed, and can easily cut apart fiber.

The present invention also provides a class yarn, staple fibre, cotton thread, tow, fiber web, compile thing, fabric, nonwoven fabric and with they similar fiber assemblies, this fiber assembly is to be mixed with other natural decomposition fibers (Y) different with it by core-sheath composite fibre (X), said core-sheath composite fibre (X) be with the crystallinity aliphatic poly ester polymer (A) of fusing point more than 140 ℃ as epidermis, will contain fusing point and constitute as the core silk than the above polymer (C) of low aliphatic poly ester polymer (B) the 10 weight % more than 20 ℃ of this polymer (A) as composition.

Brief Description Of Drawings

Fig. 1 is the cross-sectional view of the various forms of expression composite fibre of the present invention, Figure 1A is a parallel composite fiber, Figure 1B is that eccentric core-sheath composite fibre, Fig. 1 C are that key-hole type composite fibre, Fig. 1 D are the core-sheath composite fibre of eccentric two core silk types, Fig. 1 E is non-circular parallel composite fiber, Fig. 1 F is the hollow parallel composite fiber, and Fig. 1 G is 3 layers of parallel composite fiber.

Fig. 2 is become the cross-sectional view of the various forms of compound silk of the present invention by 2 kinds of mixed with fibers for expression, the compound silk of Fig. 2 A for evenly mixing by 2 kinds of circular cross-section fibers, Fig. 2 B is by 2 kinds of inhomogeneous compound silks that mix of circular cross-section fiber eccentricity, Fig. 2 C is by 2 kinds of inhomogeneous compound silks that mix of circular cross-section fiber oncentricity, the compound silk of Fig. 2 D for evenly mixing by triangular-section fiber and circular cross-section fiber, Fig. 2 E is that Fig. 2 F is by the triangular-section fiber by triangular-section fiber and the inhomogeneous compound silk that mixes of circular cross-section fiber oncentricity, the compound silk that circular cross-section fiber and the third mixed with fibers form.

Fig. 3 is the cross-sectional view of the various forms of the divisible composite fibre of expression the present invention, Fig. 3 A is 3 layers of parallel composite fiber, Fig. 3 B is 5 layers of radial pattern composite fibre, Fig. 3 C is 9 layers of radial pattern composite fibre, Fig. 3 D is 9 layers of parallel composite fiber, Fig. 3 E is a petal-shaped radial pattern composite fibre, the composite fibre of Fig. 3 F for combining by parallel type and radial pattern, Fig. 3 G is non-circular radial pattern composite fibre, Fig. 3 H is non-circular property composite fibre arranged side by side, Fig. 3 I is a hollow radial pattern composite fibre, and Fig. 3 J is the core-sheath composite fibre that 7 core silks are arranged, and Fig. 3 K is an islands-in-sea bicomponent fibre.

Fig. 4 is for representing the present invention's cross-sectional view of the various forms of caking property composite fibre voluntarily, Fig. 4 A is the core-sheath composite fibre of circular cross-section, Fig. 4 B is the core-sheath composite fibre of noncircular cross section, and Fig. 4 C is rotation symmetric form composite fibre, and Fig. 4 D is a hollow core skin composite fibre.

Fig. 5 is the cross-sectional view of the core skin composite fibre of formation fiber assembly of the present invention, and Fig. 5 A is a concentric circles core skin composite fibre, and Fig. 5 B is non-circular concentric core skin composite fibre, and Fig. 5 C is a hollow concentric circles core skin composite fibre.

Fig. 6 is a cross-sectional view embodiment of fiber assembly of the present invention, that make the silk that the different multiple mixed with fibers of shrinkage forms, the compound silk of Fig. 6 A for evenly mixing by composite fibre 4 and other fibers 5, Fig. 6 B compound silk that the two mixes with core-sheath of serving as reasons, Fig. 6 C is for by composite fibre 4 and two kind of other fiber 5 and 6 totally three kinds of compound silks that fiber mixes side by side.

Fig. 7 for measure with sweep type differential heat instrument (DSC), heat release and the absorb heat melting curve (DSC curve) of polymer when heating up be shown.

Fig. 8 for measure with sweep type differential heat instrument (DSC), the mixture or heat release and the absorb heat melting curve (DSC curve) of block copolymer when heating up that are made of two kinds of different crystallinity aliphatic polyesters of fusing point be shown.

The specific embodiment

Herein, aliphatic polyester is meant that containing the polyester that the manufacturing raw material by following aliphatic polyester obtains as main component (promptly contains more than the 50 weight %, more than the preferred 60 weight %, more preferably more than the 70 weight %), the manufacturing raw material of aliphatic polyester is (1) glycollic acid, lactic acid, hydroxy alkyl carboxylic acids such as hydroxyl butyl carboxylic acid, (2) glycolide, lactide, butyrolactone, aliphatic lactones such as caprolactone, (3) ethylene glycol, propylene glycol, butanediol, aliphatic diols such as hexylene glycol, (4) diethylene glycol, triethylene glycol, the ethylene propylene glycol, the oligomer of polyalkylene ethers such as dihydroxy ethyl butane, polyethylene glycol, polypropylene glycol, poly alkylene glycol such as polybutylene ether, (5) polytrimethylene carbonate, polytetramethylene carbonate diol, poly-carbonic acid hexylene glycol ester, poly-carbonic acid ethohexadiol ester, polyalkylene carbonate diol ester and oligomer thereof such as poly-carbonic acid decanediol ester, (6) succinic acid, adipic acid, suberic acid, azelaic acid, decanedioic acid, the polyester of aliphatic dicarboxylic acids such as decane dicarboxylic acid etc. comprises the homopolymers of all aliphatic polyesters, the block copolymer of aliphatic polyester and random copolymer, and with block copolymer or the random copolymer and/or the mixture of the following composition of other 50 weight % in aliphatic polyester; Wherein, said other compositions comprise for example aromatic polyester, polyethers, Merlon, polyamide, polyureas, polyurethane, organopolysiloxane etc.

By copolymerization or mix the purpose that aliphatic polyester is carried out modification, can enumerate and reduce crystallinity, reduction fusing point (reducing polymerization temperature or forming temperature), improvement coefficient of friction, flexibility and resilience, reduction or improve heat resistance, glass transition temperature and heat-shrinkable, improvement dyeability, hydrophily or hydrophobicity, raising or inhibition decomposability etc.

Herein, fusion caloric receptivity (melting caloric) uses sweep type differential heat instrument (hereinafter referred to as DSC), in nitrogen, is under 10 ℃/minute the condition, to measure and carried out abundant stretching, heat treatment and dry sample at programming rate, and sample weight is about 10mg.Among Fig. 7, the DSC curve is shown roughly.Fig. 7 measures example for uncrystallized sample almost, and 19 for the baseline that is caused by glass transition changes, crystallization exothermic peak that heating when measuring produces that 20 serve as reasons, 21 endothermic peaks for forming because of the crystallization fusion.For the sample of sufficient crystallising, exothermic peak 20 disappears, and is invisible.Among the present invention, the temperature of the minimum (central value) of the endothermic peak 21 that the crystallization fusion is formed is as fusing point, and total caloric receptivity (oblique line of integrated value and Fig. 7 area partly is proportional) of endothermic peak 21 is recepted the caloric as fusion.The unit of caloric receptivity is J/g.Exist in mixture or the block copolymer etc. under the occasion of several fusing points, with peak melting point as (among the present invention) fusing point.But, under some occasion, about if the fusion at the peak of maximum temperature recepts the caloric for example below the 2J/g, then can ignore not-time, if be a fusion for example big main peak more than the 20J/g that recepts the caloric, then regard actual fusing point (temperature that polymer extremely softens, begins to flow) as its main peak under the low temperature lower than maximum temperature.And the fusion caloric receptivity is the total amount of all fusion endothermic peaks.

Fiber (I) at first is described, it comprises the fibre composition that (A) is made of the aliphatic poly ester polymer of fusing point more than 100 ℃, more than the melting caloric 30J/g, and (B) by fusing point more than 100 ℃, and the fibre composition that constitutes of the melting caloric aliphatic poly ester polymer above than the little 5J/g of melting caloric of polymer (A).

This fiber (I) can be composite fibre (conjugate fiber) form that composition (A) and composition (B) are engaged in filament, the compound silk form that also can be the fiber (A) that makes composition (A) mix with the fiber (B) of composition (B).

Composite fibre of the present invention (I) is that little these the two kinds of composition polymer of polymer (B1) compound (joint) that recept the caloric when the big polymer (A1) of caloric receptivity is with fusion when making fusion form.

The composition that polymer (A1) is the crystallinity height, heat-shrinkable is little.As preferred polymer (A1), can enumerate the crystallinity homopolymers and with destroy hardly its crystalline degree copolymerization and/or mixing a small amount of (for example 40 weight % following about, particularly 30 weight % are following) second kind of composition and the third composition and polymer of forming.Fiber of the present invention is from crimpiness, intensity, stable on heating viewpoint, and polymer (A1) must be more than the 30J/g, more than the preferred 35J/g, more than the preferred especially 40J/g at the fusion caloric receptivity.The fusion caloric receptivity of crystallinity aliphatic poly ester homopolymer is about 50J/g under most occasions.Similarly, from the viewpoint of practicality, the fusing point of polymer (A1) is necessary more than 100 ℃, and is preferred more than 110 ℃, preferred especially more than 130 ℃, more preferably more than 140 ℃, most preferably more than 150 ℃.

Preferred embodiment as polymer (A1) can be enumerated, poly butylene succinate (about 116 ℃ of fusing point), poly (l-lactic acid) (about 175 ℃ of fusing point), poly-D-lactic acid (about 175 ℃ of fusing point), poly butyric ester (about 180 ℃ of fusing point), polyglycolic acid homopolymers such as (about 230 ℃ of fusing points) and copolymerization or the polymer of a small amount of other compositions of mixing and their mixture in them.In the block copolymerization, the variation of crystallinity and fusing point is slow, and the ratio of copolymer composition is preferred below 50%, be 1～40% especially, is preferably 1～30% under most occasions.In the random copolymerization, being changed significantly of crystallinity and fusing point, the ratio of copolymer composition is preferably 0.5～10%, is preferably 1～5% especially.Certainly, fusing point and crystalline variation by copolymerization causes have very big variation according to copolymer composition is different, so are necessary to be careful crystallization fusion caloric receptivity and the fusing point of being measured by DSC.By mixing fusing point and the crystalline variation that other compositions cause, also sizable variation is arranged because of blending constituent and mixing ratio, in most cases, there is not random copolymerization remarkable.The consumption of other compositions that are used for copolymerization and mix under the situation of not destroying the object of the invention, is selected in above-mentioned scope.For example can enumerate the raw material of aliphatic polyester, aromatic polyester, polyethers, Merlon, polyamide, polyureas, polyurethane, organopolysiloxane or these polymer such as polyester that generates by aliphatic dicarboxylic acids such as aliphatic diol such as ethylene glycol, ethohexadiol and succinic acid, decane dicarboxylic acids and polycaprolactone etc. as other compositions.

Polymer (B1) is the composition that crystallinity is low, heat-shrinkable is big.As the polymer (B1) that is suitable for, can enumerate the aliphatic polyester that the method that adopts copolymerization or mixing has reduced the fusion caloric receptivity of crystallization.The fusion caloric receptivity of the fusion caloric receptivity of polymer (A1) and polymer (B1) must differ more than the 5J/g, and is curling strongly in order to make fiber, preferably differs more than the 10J/g, especially preferably differs more than the 15J/g.Should illustrate, 5J/g be about crystallinity aliphatic poly ester homopolymer fusion caloric receptivity 10%.That is, the degree of crystallinity of polymer (B1) is about below 90% of polymer (A1) degree of crystallinity.

Usually, need preferred strong the curling such as volume thing of big retractility, in order to provide pliability, bulkiness and excellent handle to fabric etc., what preferably be subjected to sometimes to a certain degree suppressing curls, can be according to application target selective polymer (B1).In addition, from the viewpoint of practicality, the fusing point of polymer (B1) must be more than 100 ℃, and is preferred more than 110 ℃, preferred especially more than 130 ℃, most preferably more than 135 ℃.As the higher polymer of this fusing point, can enumerate with the copolymer (block copolymer, random copolymer) or the mixture of above-mentioned high-melting-point homopolymers as main component (more than the 50 weight %).Be used for and high-melting-point homopolymers copolymerization such as poly butylene succinate, PLA, poly butyric ester, polyglycolic acid or the composition that mixes, can make the raw material from above-mentioned aliphatic polyester and select aptly.

As with the preferred embodiment of homopolymer block copolymerization or the composition that mixes, can be that glass transition temperature is below normal temperature, particularly at the aliphatic polyester below 0 ℃, for example except that polycaprolactone, can also enumerate by the ethylene glycol more than a kind, propylene glycol, butanediol, hexylene glycol, ethohexadiol, diethylene glycol, aliphatic diol class and the succinic acid more than a kind such as triethylene glycol, adipic acid, decanedioic acid, the octane dicarboxylic acids, the polyester that aliphatic dicarboxylic acids such as decane dicarboxylic acid combine, for example polyethylene glycol succinate, poly butylene succinate, polyethylene glycol adipate, poly adipate succinic acid ester, polyethylene glycol sebacate, polydiethylene glycol sebacate etc.

Polymer (B1) must be above-mentioned the sort of low-crystalline.The effective method that makes that crystallinity reduces is random copolymerization.Example as the easy random copolymerization of energy, can enumerate the optical isomer that makes L-lactic acid/D-lactic acid, L-lactide (LL lactide)/D-lactide (DD lactide, DL lactide), lactic acid/glycollic acid, lactide/glycolides, lactide/caprolactone etc., the combination of variety classes hydroxycarboxylic acid, the method for copolymerization more than 2 kinds such as the combination of variety classes lactone or hydroxycarboxylic acid, glycol, dicarboxylic acids etc.Also preferred random copolymer and above-mentioned block copolymer or mixture of polymers not of the same race.As the variety classes polymer, can enumerate for example aromatic polyester, polyethers, Merlon, polyamide, polyureas, polyurethane, organopolysiloxane etc.

Polymer (B1) can not be crystalline also.Under noncrystalline occasion, the temperature when fusing point uses melt viscosity to become 100,000 pools.

Polymer (A1) must be an eccentric structure with the composite construction of polymer (B1).Eccentric structure is meant the center of gravity of polymer in cross section (A1) and the inconsistent relation of center of gravity of polymer (B1).The center of gravity of two compositions is at a distance of far away more, and eccentricity is high more, and crimpiness is strong more.Can select eccentric composite construction miscellaneous according to the purpose crimpiness of wanting to reach.

Figure 1A～1G is the composite fibre cross section of the instantiation of the preferred composite construction of expression the present invention.Among the figure, 1 is polymer (A1), and 2 is polymer (B1), and 3 is the hollow part.Figure 1A is the high example of the eccentricity of parallel type, Figure 1B is the low example of the eccentricity of eccentric core-sheath, and Fig. 1 C is that key-hole type composite fibre, Fig. 1 D are that eccentric 2 core silk type composite fibres, Fig. 1 E are that non-circular parallel composite fiber, Fig. 1 F are that hollow parallel composite fiber, Fig. 1 G are 3 layers of parallel composite fiber.In certain composite construction beyond Figure 1A～1G,, also can be applied to the present invention with the fiber of the eccentric configuration of two compositions.And, except polymer (A1) and polymer (B1), can also compound the third composition.For example, can dispose the third polymer in the hollow part of Fig. 1 F.

There is no particular limitation for the compound ratio (sectional area ratio) of polymer (A1) and polymer (B1), can select arbitrarily according to purpose.Usually, compound ratio is that 1/1 o'clock crimpiness is the strongest as Figure 1A, and compound ratio is from 1/1 far away more, and crimpiness is weak more.Under most occasions, compound ratio is 1/10～10/1, especially, is preferably 1/5～5/1, most preferably is 1/3～3/1.

There is no particular limitation for the difference of the shrinkage factor of polymer during spinning fibre (A1) and polymer (B1), common more than 3%, especially, is preferably 5～70%, most preferably is about 10～50%.

Under most occasions, the mutual cohesiveness height of preferred polymers (A1) and polymer (B1), even but lack cohesiveness, if become the core-sheath structure, also can prevent to peel off.In addition, for example, it is compound that the fiber a little less than the cohesiveness is pressed parallel type etc., after making braided fabric etc. two compositions peeled off, and can obtain the fibre of the very thin softness of noncircular cross section.Under this occasion, the different contraction that is caused by the shrinkage difference of two kinds of compositions mixes fine effect, can provide good hand feeling to goods.

The cross section of composite fibre of the present invention (I) can be selected circle, Long Circle, Pear-Shaped, polygon, compound leaf shape, alphabetical shape etc. various non-circular (abnormity), hollow shape etc. arbitrarily.Fiber number is to select arbitrarily according to application target too, but usually dress material is about 0.1～50 dawn (d) with the filament number of fiber, especially, is preferably 0.5～30d.During using etc., nonwoven fabric, leather, material use thinner or thicker fiber.

Composite fibre of the present invention can adopt fusion, wet type, dry type, dry-and wet-type and other method, polymer (A1) and polymer (B1) is carried out composite spinning make, and particularly melt spinning efficient height is preferred.Melt spinning can be that winding speed is the low speed spinning that 500～2000m/ divides, and can be that winding speed is the high speed spinning that 2000～5000m/ divides, and also can be that winding speed 5000m/ divides above super high-speed spinning, can stretch as required or heat treatment.Usually, the stretching about 3～6 times is carried out in the low speed spinning, and high speed spinning carries out the stretching about 1.5～2.5 times, and super high-speed spinning does not need to stretch or carry out stretching following about 2 times.The so-called spinning drawing-off mode that also can preferably adopt spinning and stretch and carry out continuously.

In addition, can polymer (A1) and polymer (B1) is compound, from the spun while of spinneret orifice, adopt the methods such as メ Le ト Block ロ-Fa, flash spinning, spun-bond process that melt and spray of nonwoven fabricization.

Composite fibre of the present invention can form form arbitrarily such as continuous filament yarn, monofilament, multifilament, cut-out staple fibre according to application target.In addition, in the operation of spinning fibre or yarn, perhaps after making fiber structures such as compiling thing, fabric, nonwoven fabric, can adopt means such as heating or swelling to make its contraction, curl voluntarily.Certainly, also can adopt false twisting or indentation method etc. that it is curled with yam-like as required, heating be curled it voluntarily then.For example, it is curled voluntarily.Add that thermal recovery is xeothermic, damp and hot, infrared ray and other any means carry out.Usually, curl voluntarily and carry out with relaxed state mostly, control curling but can apply appropriate tension force.Necessary curling intensity is according to application target and difference, and there is no particular limitation, and under most occasions, curling extensibility is preferably more than 50%, and is preferred especially more than 100%, most preferably more than 150%, and the most widely-used about 100～600%.

Compound silk of the present invention (I) is the big polymer (A1) of time caloric receptivity is made by fusion fiber (A) complex between the two fiber that mixes of fiber (B) that little polymer (B1) makes that recepts the caloric during with fusion.

Three Represents as compound silk instantiation of the present invention is, the mixed filament (hereinafter referred to as " mixed yarn ") that mixes by several continuous filament yarns, " length/weak point compound silk " that be composited by continuous filament yarn and staple fibre, and " blended ratio " that form by several staple fibre mix spinnings.As everyone knows, the past is in compound between these fibers (mixing) thing, and the fiber combinations that shrinkage is different obtain bulkiness and the good goods such as braided fabric of flexibility together.But, for the aliphatic poly ester fiber, almost also do not understand the inotropic method of control, moreover do not know the fiber composite that shrinkage is different fully, or improve the quality of fabric or volume thing with its.Present inventors have furtherd investigate the improvement of the qualities such as braided fabric of aliphatic poly ester fiber, find, the shrinkage of the fiber (A) that the big polymer (A1) of caloric receptivity is made during by fusion when heating is little, and the shrinkage of the fiber (B) that the little polymer (B1) of time caloric receptivity is made by fusion when heating is big, these two is combined, can obtain the fiber with excellent works.Especially, different by making fiber (A) with the shrinkage factor of fiber (B), can obtain the goods of good hand.

The polymer that constitutes the fiber (A) of compound silk (I) is the composition that the fusion caloric receptivity is big, heat-shrinkable is little, can use and the identical composition of above-mentioned polymer (A1).

The composition that the polymer that constitutes the fiber (B) of compound silk (I) is a low-crystalline, the fusion caloric receptivity is little, heat-shrinkable is big can use and the identical composition of above-mentioned polymer (B1).Goods for the excellent handle that obtains to cause by sufficient shrinkage factor difference, the fusion caloric receptivity of the fusion caloric receptivity of polymer (A1) and polymer (B1) must differ more than the 5J/g, preferably differs more than the 10J/g, especially preferably differ more than the 15J/g, most preferably differ more than the 20J/g.Usually, need the braided fabric of big bulkiness, retractility and flexibility etc., the combination of preferred shrinkage factor difference big (for example 20～50%), and for bulkiness or the excellent handle that is subjected to a certain degree suppressing is provided, the also preferably combination of shrinkage factor difference little (5～20%) can be according to application target selective polymer (B1).And from the viewpoint of practicality, the fusing point of polymer (B1) is necessary for more than 100 ℃, and is preferred more than 110 ℃, preferred especially more than 130 ℃, most preferably more than 135 ℃.

Respectively polymer (A1) and polymer (B1) are spun into fiber, make molecularly oriented with stretching, heat treatment etc. as required, thereby make fiber (A) and fiber (B).Can adopt various means that fiber (A) and fiber (B) are mixed, obtain compound silk of the present invention (fibre blend).There is no particular limitation for mixed method, fiber (A) and fiber (B) are all under the occasion of long filament, preferred use from the spinning of spinning silk winding simultaneously of same or contiguous spinning head mix method for fiber, respectively after the spinning with air nozzle etc. carry out air mix fine method, only be doubling, and twist with the fingers, mix fine false twisting methods such as (composit false twistings).One side of fiber (A) and fiber (B) is that long filament, the opposing party are under the occasion of staple fibre, can use the what is called bag core silk spinning yarn method of supplying with long filament in spinning process.Fiber (A) and fiber (B) are all under the occasion of staple fibre, adopt methods such as common mixing cotton, mixing sliver, blended fiber net can obtain blended ratio easily.

Fig. 2 A～2F is the cross-sectional view that the instantiation of combined yarn, bag core silk (length/single compound silk) and blended ratio is shown.Among the figure, 4 is fiber (A), and 5 is fiber (B), and 6 is other fibers (C).Fig. 2 A is for making 12 circular cross-section fibers (A) and the more mixed uniformly example of 12 circular cross-section fibers (B), Fig. 2 B is for making the example of 12 circular cross-section fibers (A) and 12 circular cross-section fibers (B) eccentric (center of gravity is in state disconnected from each other separately) configuration, Fig. 2 C for make 10 circular cross-section fibers (B) inner, make the externally example of concentric arrangement of 14 circular cross-section fibers (A).Fig. 2 D is for making 12 circular cross-section fibers (B) and the roughly mixed uniformly example of 15 triangle section fibers (A), Fig. 2 E is for making 6 examples of crude fibre (B) and 15 thin slightly triangle section fiber (A) core-sheaths configurations slightly, and Fig. 2 F is for making 4 crude fibre (B) and the fine fibre (A) of 12 triangle sections, the examples that mix with other 12 circular cross-section fibers (C) again slightly.

Among the present invention, there is no particular limitation for the blending ratio (weight ratio) of the cross sectional shape of fiber, fiber number, fiber (A) and fiber (B) etc., can at random select.The blending ratio of fiber (A) and fiber (B) can be selected according to the purpose goods, is 10/1～1/10, is preferably 5/1～1/5, and more preferably 3/1～1/3, most preferably 2/1～1/2.Fiber (A) is also unqualified with compound (mixing) state of fiber (B), in most cases be extensive use of basically and preferably and as Fig. 2 A, make the two state even and random dispersion, the state of eccentric configuration as Fig. 2 B, the state of core skin or concentric arrangement is these three kinds as Fig. 2 C.And, also can as Fig. 2 F, mix other fibers (C).As fiber (C), wool, cotton and the aliphatic poly ester fiber etc. of preferred especially natural decomposition.

Past, particularly in the coat that needs flexibility, jacket, underwear, the clothing, the braided fabric of upper garment and flimsy material in addition or intermediate gauge etc., in the dyeing and finishing manufacturing procedure, extensively carry out a kind of alkali decrement processing, promptly, handle the cloth that is made into by polyester fiber with highly basic (sodium hydrate aqueous solution etc.), the part of polymer (for example 5～50%, particularly 10～30%) is decomposed and removed.The aliphatic poly ester fiber also can carry out the processing of alkali decrement.But usually, the aliphatic poly ester fiber is extremely responsive to alkali, compares with the aromatic polyester fiber in past, (low alkaline concentration, low pH, low temperature etc.) carry out under the condition of milder.In the alkali decrement processing of the braided fabric that uses compound silk of the present invention, fiber (B) is compared with fiber (A), has alkali decrement speed to be inclined to faster.Therefore, under the occasion of specifying the alkali decrement, according to the decrement speed of fiber (B), its monofilament (on average) fiber number is bigger than fiber (A), and is for example more than 10%, big like that about preferred especially 20～400% (5 times).Additive method as same purpose, can enumerate the cross section that makes fiber (B) is to press the little circular or cross section similar with it of the shared surface area of per unit weight, the cross section that makes fiber (A) is, the particularly polygon of high surface area about 20～400% (5 times) or the method for compound leaf shape also bigger more than 10% than it, preferably after alkali decrement processing, make fiber (A) as far as possible and (B) be in suitable fiber number and blending ratio respectively.Certainly, also can merge above-mentioned 2 methods of using.But, to carry out under the occasion of alkali decrement processing, the alkali decrement of aliphatic poly ester fiber is processed a big advantage that has and is, and the consumption of alkali is few, and the analyte of generation (lactic acid etc.) is easily by biological decomposition, and is therefore few to the adverse effect of environment.

There is no particular limitation for the difference of the boiling water shrinkage of fiber (A) and fiber (B) (in 100 ℃ of boiling water, handling 10 minutes down zero load, when the indoor air dry of normal temperature), usually differ more than 3%, especially, preferably differ about 5～50%, the most extensive employing differs about 10～40%.Therefore, the boiling water shrinkage of fiber (A) is preferred below 15%, and is preferred especially below 10%.On the other hand, the boiling water shrinkage of fiber (B) is preferred more than 15%, and is preferred especially more than 20%, is extensive use of about 30～60%.

Shapes such as circle, Long Circle, Pear-Shaped, polygon, compound leaf shape, alphabetical shape and other various non-circular (abnormity), hollow shape can be at random selected in the cross section of fiber (A) and fiber (B).Fiber number is to select arbitrarily according to application target too, but usually dress material is about 0.1～50d with the filament number of fiber, especially, is preferably 0.5～30d, the scope of widely-used 1～20d.During using etc., nonwoven fabric, leather, material use thinner or thicker fiber.Fiber (A) and fiber (B) also can be that the mixed with fibers more than 2 kinds that cross section, fiber number, shrinkage factor is different respectively forms.

Compound silk of the present invention (I) can adopt fusion, wet type, dry type, dry-and wet-type and other methods, and polymer (A1) and polymer (B1) spinning are made, and especially, melt spinning efficient height is preferred.Melt spinning can be that winding speed is the low speed spinning that 500～2000m/ divides, can be that winding speed is the high speed spinning that 2000～5000m/ divides, also can be that winding speed 5000m/ divides above super high-speed spinning, can also stretch as required or heat treatment.Usually, the stretching about 3～8 times is carried out in the low speed spinning, and high speed spinning carries out the stretching about 1.5～3 times, and super high-speed spinning does not need to stretch or carry out stretching following about 2 times.The so-called spinning drawing-off mode that also can preferably adopt spinning and stretch and carry out continuously.In addition, fiber (A) also can preferably use a kind of special " elongation silk voluntarily ", and it is the fiber that stretches, heat-treats at low temperatures with than low range, in subsequent handling, carries out crystallization and orientation through heat, makes elongate fiber.

Compound silk of the present invention can be continuous filament yarn combined yarn and twisted filament, composit false twisting silk, blended ratio and with their similar silks etc., can be any form according to application target, can make with them and compile thing, fabric, nonwoven fabric and other fiber structure.In their manufacturing process and manufacturing procedure, perhaps after making, heat aptly or swelling, make the shrinkage factor between fiber (A) and the fiber (B) produce difference thus, can provide good bulkiness, flexibility, retractility and feel to goods.Heating can be xeothermic, damp and hot, infrared ray or these methods be merged other any means of using.Solvent, swelling agent or water are used in swelling.Certainly, also can adopt as required with yam-like false twisting or indentation method etc., it is curled, heating makes its contraction then.In addition, in the dyeing and finishing manufacturing procedure of for example fabric or volume thing, can extensively carry out heat shrink in ground.Usually, shrink process is many carries out with relaxed state, controls contraction but can apply appropriate tension force.

Fiber (II) below is described, it comprises fibre composition that the crystallinity aliphatic poly ester polymer of (A) fusing point more than 140 ℃ forms and (B) the crystallinity aliphatic polyester composition (H) of fusing point more than 110 ℃ and fusing point below 120 ℃ and than low crystallinity aliphatic polyester or the fibre composition that is combined to form at the amorphism aliphatic polyester composition (S) below 30 ℃ of glass transition temperature more than 10 ℃ of the fusing point of above-mentioned polymer (A).

This fiber (II) can be the composite fibre form that composition (A) and (B) are engaged in filament, also can be that each composition is through the fiber (A) of molecularly oriented and the compound silk form that (B) mixes.In addition, the aliphatic polyester composition (H) in the fibre composition (B) and (S) can be the block copolymer form of two kinds of composition combinations also can be two kinds of mixture of ingredients forms.

Fibre composition (A) in the fiber (II) is the little composition of heat-shrinkable, and the fusing point that is used for the crystallinity aliphatic poly ester polymer (A2) of fibre composition (A) must be more than 140 ℃, and is preferred more than 150 ℃, more preferably more than 160 ℃, preferred especially more than 170 ℃.In addition, preferably its fusion caloric receptivity is big, more than the preferred 20J/g, more preferably more than the 30J/g, more than the preferred especially 40J/g.Example as this high crystalline, dystectic aliphatic polyester, can enumerate poly (l-lactic acid) (about 175 ℃ of fusing point), poly-D-lactic acid (about 175 ℃ of fusing point), poly 3-hydroxy butyrate (about 180 ℃ of fusing point), polyglycolic acid (about 230 ℃ of the fusing point) homopolymers of etc.ing and copolymerization or mix on a small quantity (below the preferred 50 weight % in these homopolymers, more preferably below the 40 weight %, preferred especially 30 weight % are following) polymer of other compositions.There is no particular limitation for the weight average molecular weight of polymer (A2), from the viewpoint of practicality, is preferably more than 50,000, especially preferred 70,000～300,000, and more preferably 80,000～300,000, preferred especially 80,000～200,000, preferred more especially 100,000～200,000.

Usually, in the block copolymerization, the variation of crystallinity and fusing point is slow, and the ratio of the copolymer composition in the polymer (A2) can be 1～50 weight %, further be 1～40 weight %, 1～30 weight % particularly, and in the random copolymerization, being changed significantly of crystallinity and fusing point, the ratio of copolymer composition is preferably 0.5～20 weight %, more preferably 0.5～10 weight % is preferably 1～10 weight % especially, more special 1～5 weight % that is preferably.Certainly, the fusing point or the crystalline variation that cause because of copolymerization have very big variation according to copolymer composition is different, so must be careful crystallization fusion caloric receptivity and fusing point that DSC measures.Because of mixing fusing point or the crystalline variation that other compositions cause, also sizable variation is arranged, but in most cases, do not have random copolymerization remarkable according to blending constituent or mixing ratio.As other compositions that are used for above-mentioned homopolymers copolymerization or blend, for example can enumerate aliphatic polyester or its raw material, aromatic polyester, polyethers, Merlon, polyamide, polyureas, polyurethane, organopolysiloxane etc. as mentioned above such as the polyester that generates by aliphatic dicarboxylic acids such as aliphatic diol such as ethylene glycol, ethohexadiol and succinic acid, decane dicarboxylic acids and polycaprolactone.

A preferred configuration fiber (IIa) of fiber (II), comprise (A2) by fusing point more than 140 ℃ and the fibre composition that constitutes of the crystallinity aliphatic poly ester polymer more than the fusion caloric receptivity 20J/g, and (B2) differ the block copolymer of at least 2 kinds of aliphatic polyesters more than 10 ℃ and/or the fibre composition that mixture constitutes by fusing point; Wherein, said block copolymer and/or mixture contain high-melting-point composition (H) 95～10 weight %s of fusing point more than 110 ℃, more than the fusion caloric receptivity 3J/g, and fusing point is 40～120 ℃, above low melting point composition (S) 5～90 weight % of fusion caloric receptivity 3J/g.

This fiber (IIa) can be that composition (A2) engages the formation composite fibre with (B2) in filament, also can be fiber (A2) to be mixed with (B2) each composition form compound silk, but at first the occasion of making compound silk be described.

Compound silk of the present invention (IIa) is a complex between a kind of fiber, it be by the low-shrinkage fiber (A2) that is spun into fusing point more than 140 ℃, high crystalline aliphatic poly ester polymer (A2) more than the fusion caloric receptivity 20J/g with mix with containing the high-melting-point composition (H) and the highly shrinkable fiber (B2) that is spun into of the aliphatic polyester (B2) of the fusing point low melting point composition (S) that is 40～120 ℃ of fusing point more than 110 ℃.Three Represents as compound silk instantiation of the present invention is, the mixed filament (combined yarn) that is mixed by several continuous filament yarns, " length/weak point compound silk " and " blended ratio " that is formed by several staple fibre mix spinnings that are composited by continuous filament yarn and staple fibre.

In the compound silk (IIa), polymer (A2) is the composition that fusing point and fusion caloric receptivity is high, heat-shrinkable is little.As preferred polymer (A2), can enumerate the crystallinity homopolymers and to destroy its crystalline degree copolymerization hardly and/or to mix the copolymer or the mixture of a small amount of (for example below the 40 weight %, particularly 30 weight % are following) second kind of composition or the third composition.From the viewpoints such as intensity, heat resistance and goods feel of fibre blend of the present invention (IIa), polymer (A2) fusion caloric receptivity must be more than the 20J/g, more than the preferred 30J/g, more than the preferred especially 40J/g.The fusion of crystallinity aliphatic poly ester homopolymer caloric receptivity is about 50J/g or higher under most occasions.

Aliphatic polyester (B2) is for fusing point differs from least 2 kinds of aliphatic polyesters (H) and block copolymer (S) and/or mixture more than 10 ℃, contains high-melting-point composition (H) and fusing point low melting point composition (S) 95～10 weight %s and the 590 weight %s that are 40～120 ℃ of fusing point more than 110 ℃ respectively.Composition (H) is used to keep the heat resistance of aliphatic polyester (B2), and fusing point is necessary more than 110 ℃, and is preferred more than 120 ℃, preferred especially more than 140 ℃.The weight ratio of composition (H) is 95～10%, is preferably 85～20%, more preferably 75～30%.The fusion of composition (H) caloric receptivity must more than the preferred 5J/g, more preferably more than the 10J/g, be preferably about 10～50J/g more than the 3J/g especially in the aliphatic polyester (B2).

Because wish that by the composition (S) in the aliphatic polyester (B2) be the composition that the heat-shrinkable to the fiber (B2) that is spun into by this polymer (B2) works, fusing point is necessary for 40～120 ℃, is preferably 50～110 ℃, more preferably 60～100 ℃.In the polyester (B2), the ratio of composition (S) is 5～90 weight %, is preferably 1580 weight %, more preferably 25～70 weight %.

The fusing point of composition (S) must hang down 10 ℃ at least than the fusing point of composition (H), and its fusing point difference is preferably more than 20 ℃, more preferably more than 30 ℃.For example, with fusing point is that 160 ℃ composition (H) and fusing point is the fiber that the block copolymer that constitutes of 80 ℃ composition (S) or mixture are spun into, if for example handling in 100 ℃ of water, then owing to composition (S) fusion produces very big contraction, but owing to there is high-melting-point composition (H), not fusion of fabric integer has kept shape.Therefore, can wait the composition (H) of selecting to constitute polyester (B2), the fusing point and the ratio thereof of (S) according to necessary heat treatment temperature, heat-shrinkable and heat resistance.Usually, low melting point composition (S) can be a low-crystalline, if but crystallinity is low excessively, and then the dyefastness of fiber reduces, and bonding through generations such as heating.Therefore, the fusion under the temperature (for example 80～120 ℃) of the heat treatment step that makes its contraction, preferred temperature (for example below 40 ℃) in use is sufficient crystallisingization down.That is, under most occasions, composition (S) is a crystallinity, and its fusing point is 50～110 ℃, especially, is preferably 60～100 ℃.Composition (S) in the aliphatic polyester (B2), its crystallization fusion caloric receptivity must be more than 3J/g, more than the preferred 5J/g, more preferably about 10～40J/g.

Aliphatic polyester (B2) by main composition composition (H) with (S) block copolymerization and/or mix.Lactones such as caprolactone, lactide, glycolide, the aliphatic polyester that easily has a hydroxyl with molecular end under molten condition carries out addition reaction (polymerization), the acquisition block copolymer.In addition, also can make bifunctional compound such as dicarboxylic acids halide such as dicarboxylic acids acid anhydrides, paraphthaloyl chlorides such as vulcabond, phthalic anhydride such as two isocyanic acid hexylene glycol esters for example and molecular end have the aliphatic polyester more than 2 kinds of hydroxyl mixture reaction, it is combined, obtain block copolymer.Similarly, also can make several aliphatic polyester melting mixing, carry out ester exchange reaction and obtain block copolymer.But if in the presence of the catalyst and too carrying out melting mixing for a long time under the high temperature, then ester exchange reaction excessively becomes random copolymer, therefore must give one's full attention to.

Composition (H) and mixing of (S) can be that their particle is mixed, carries out fusion and mixing with screw extruder etc., also can be to use a kind or several being used in combination of double screw extruder and other agitating devices, static mixer etc., with two kinds of compositions mixing of fusion respectively; Said static mixer can carry out cutting apart and converging of logistics in multistage ground repeatedly.Under this occasion, must be noted that also ester exchange reaction can not be excessive.With dsc analysis mixture or reactant,, then can judge how not carry out atactic polymerization if fusing point and fusion caloric receptivity do not reduce.For composition (H) and mixed stability ground (S) are carried out, wish both compatibility height.As the method for improving both compatibilities, can enumerate with its method such as poly-of block and composition (S) part is incorporated into method in the molecule of composition (H), to composition (S) in, introduces the method for composition (H) and will be coupled to composition (H) and the medium method of mixture (S) as the block copolymer of two kinds of compositions of compatibility improver (surfactant).

Aliphatic polyester (B2) mainly constitutes by aliphatic polyester composition (H) with (S), other compositions as submember (below the 50 weight %, particularly 30 weight % are following) can contain for example aromatic component, polyether components, Merlon composition, polyurethane composition, polyamide composition, organopolysiloxane composition etc.The introducing of these other compositions can adopt the method for copolymerization or mixing to carry out.

There is no particular limitation for the molecular weight of aliphatic polyester (B2), is preferably more than 50,000, is preferably 8～300,000 especially, is extensive use of 10～200,000.

As the instantiation of the aliphatic polyester that is suitable for high-melting-point composition (H), except be used for above-mentioned polymer (A2) institute example, can also enumerate poly butylene succinate (116 ℃ of fusing points), poly-fumaric acid hexylene glycol ester (117 ℃ of fusing points) etc.

Instantiation as the polyester that is suitable for low melting point composition (S), except for example polycaprolactone (about 59 ℃ of fusing point), beyond the poly-propiolactone aliphatic poly lactones such as (about 95 ℃ of fusing points), can also enumerate by ethylene glycol, propylene glycol, butanediol, hexylene glycol, ethohexadiol, diethylene glycol, aliphatic diol classes such as triethylene glycol more than one and succinic acid, adipic acid, azelaic acid, decanedioic acid, the octane dicarboxylic acids, the polyester that more than one combinations of aliphatic dicarboxylic acids such as decane dicarboxylic acid obtain, for example polyethylene glycol adipate (about 49 ℃ of fusing point), polyethylene glycol suberate (about 65 ℃ of fusing point), polyethylene glycol azeleate (about 52 ℃ of fusing point), polyethylene glycol sebacate (about 75 ℃ of fusing point), poly butylene succinate (about 116 ℃ of fusing point), poly adipate succinic acid ester (about 72 ℃ of fusing point), polydiethylene glycol sebacate (about 66 ℃ of fusing point), poly-decanedioic acid hexylene glycol ester (about 74 ℃ of fusing point) and other homopolymers and be the block or the random copolymer of composition with them.

Respectively polymer (A2) and polymer (B2) are spun into fiber, stretch as required, heat treatment etc. makes its molecularly oriented and crystallization, makes fiber (A2) and fiber (B2).The necessary condition of the manufacture method of the compound silk (IIa) that is made of fiber (A2) and fiber (B2), processing method, each fiber, the cross sectional shape of compound silk and other necessary conditions etc. are identical with the occasion of compound silk (I).

Below describe for making composition (A2) and (B2) in the fiber (IIa) in filament, engage the occasion that forms composite fibre.

Make under the occasion of composite fibre (IIa), the fibre composition (B2) that engages with fibre composition (A2) differs at least 2 kinds of crystallinity aliphatic polyesters (H) and block copolymer (S) and/or mixture more than 20 ℃ for containing fusing point, preferably contains fusing point more than 130 ℃, above high-melting-point composition (H) 90～10 weight % and the fusing point of fusion caloric receptivity 3J/g is 40～120 ℃, low melting point composition (S) 10～90 weight % more than the fusion caloric receptivity 3J/g.This composition (H) and (S) be selected from mentioned component (H) and (S).

Make fibre composition (A2) and fibre composition (B2) in filament during eccentric the joint, can obtain the composite fibre (IIa) that crimpiness is good voluntarily, make fibre composition (B2) form composite fibre at least a portion surface and in filament, during concentric engagement, can obtain the composite fibre (IIa) that caking property is good voluntarily like that.

Among Fig. 8, summarily illustrate and be used for fusing point of the present invention and differ that several aliphatic polyesters more than 20 ℃ mix and/or the DSC curve of the aliphatic polyester (B2) that block copolymerization forms.Among the figure, 22 is the fusion endothermic peak of low melting point composition (S), and 24 is the fusion endothermic peak of high-melting-point composition (H).The crystalline exotherm peak that peak 23 (dotted line) does not observe during sufficient crystallising for high-melting-point composition (H).Because if this exothermic peak 23 overlaps with the fusion endothermic peak 22 of low melting point composition (S), then can not correctly hold fusion endothermic peak 22, so must make high-melting-point composition (H) sufficient crystallising.

Among the present invention, the temperature of each endothermic peak that fusing point causes for the crystallization fusion (among the figure 22 and 24) minimum of a value recepts the caloric other total caloric receptivity of branch (integrated value, proportional with the area of drawing the oblique line part among the figure) of endothermic peak as fusion.The unit of caloric receptivity is J/g.Exist under the occasion at several fusing points (peak), the typical value of fusing point is the highest temperature, but for example recepts the caloric below the 3J/g when the peak of maximum temperature, can ignore peak melting point in the main peak not-time, that caloric receptivity is big as typical value.

Usually, in the DSC curve of the mixture of several crystallinity aliphatic polyesters or block copolymer, majority can observe and the corresponding endothermic peak of the fusing point of each composition quite significantly.But, under the occasion of the block copolymer of several polymer, as seen changing such as each fusing point (temperature), endothermic peak broadens, and produces acromion, the complicated phenomenon of bimodal grade.When thinking that they can not be separated into several peak significantly, then regard single peak as, fusing point uses peak value.

The composite fibre of crimpiness voluntarily of the present invention (IIa) be with fusing point more than 140 ℃, more than the fusion caloric receptivity 20J/g high crystalline aliphatic poly ester polymer (A2) with contain fusing point more than 130 ℃ high-melting-point composition (H) and the aliphatic polyester (B2) of fusing point two kinds of compositions of low melting point composition (S) of being 40～120 ℃ be composited, fibre composition (A2) is low contractile element, fibre composition (B2) is high contractile element, makes the length of (A2), (B2) two compositions produce difference by heating or swelling and occurs curling.

This is being characterised in that greatly of crimpiness fiber (IIa) voluntarily, as highly shrinkable composition (B2), uses fusing point to differ more than 20 ℃, preferably differs the block copolymer and/or the mixture of at least 2 kinds of crystallinity aliphatic polyesters more than 30 ℃.In this fiber (IIa), the low melting point composition (S) that constitutes this aliphatic polyester is melted or softening and strong the contraction take place if be heated to, and high-melting-point composition (H) can not fusion or softening temperature, curling appears in then fibre composition (B2) not fusion of integral body and shrinking, fiber (IIa).Therefore, the fusing point of the high-melting-point composition (H) in the composition (B2) is high more good more, and is necessary more than 130 ℃, preferred more than 140 ℃, more preferably more than 150 ℃, most preferably more than 160 ℃.Low melting point composition (S) be crystallization at normal temperatures, through the appropriateness (for example 50～120 ℃) heating be the composition of melting, fusing point is 40～120 ℃.Usually, the curing rate of low melting point polymer when melt spinning is slow, the silk bonding mutually easily (deadlocked) of being reeled and make spinning become difficult, and aliphatic polyester (B2) is by introducing high-melting-point composition (H), deadlocked property is improved significantly, makes and becomes easy.

The crimpiness of composite fibre can be by change constituting aliphatic polyester (B2) the compositely proportional, complex morphological, heating-up temperature etc. of fusing point, composition (A2) and composition (B2) of ratio, low melting point composition (S) of high-melting-point composition (H) and low melting point composition (S), in the scope of non-constant width, control, can select suitable curling according to purpose and purposes.That is, the big feature that composite fibre of the present invention had is, can adopt melt spinning method to make expeditiously, can and regulate crimpiness in the scope inner control of non-constant width.

Separately will be when being spun into fiber as the polymer (A2) of low contractile element, its shrinkage factor in 100 ℃ of water is preferred below 20%, more preferably below 15%, especially, more preferably below 10%, most preferably below 8%.Therefore, preferred especially copolymerization of polymer (A2) or low modification degree person when mixing, homopolymers and close therewith polymer, for example the ratio of copolymer composition or blending constituent is preferred below 10%, preferred especially below 6%, the polymer below 3% most preferably.

Aliphatic polyester (B2) is for fusing point differs the block copolymer and/or the mixture of at least 2 kinds of crystallinity aliphatic polyesters more than 20 ℃, contains hard fat adoption ester composition (H) and fusing point low melting point aliphatic polyester composition (S) 90～10 weight %s and 10～90 weight %s that are 40～120 ℃ of fusing point more than 130 ℃ respectively.Because low melting point composition (S) shrinkage occurs by heating, therefore, fusing point is necessary for 40～120 ℃, is preferably 50～120 ℃, preferred especially 60～120 ℃.High-melting-point composition (H) in the aliphatic polyester (B2) is necessary for 9/1～1/9 with the weight ratio of low melting point composition (S), is preferably 8/2～2/8, is preferably 7/3～3/7 especially.High-melting-point composition (H) in the aliphatic polyester (B2) must more than the preferred 5J/g, more preferably more than the 10J/g, be preferably the scope about 10～30J/g more than the difference 3J/g especially with the fusion of low melting point composition (S) caloric receptivity.Prevent deadlocked viewpoint during from melt spinning, aliphatic polyester (B2) is preferably crystalline.

It is more than 20 ℃ that high-melting-point composition (H) in the aliphatic polyester (B2) must differ with the fusing point of low melting point composition (S), preferably differs more than 30 ℃, especially preferably differs more than 40 ℃.For example, block copolymer or mixture that the composition (S) of 80 ℃ of the composition (H) of 160 ℃ of fusing points and fusing points is combined, for example handling under 100 ℃, because of composition (S) fusion strong contraction takes place then, and, make the not fusion of fibre composition (B2) integral body keep shape owing to there is the high-melting-point composition (H) of crystallization.

Separately aliphatic polyester (B2) is spun under the occasion of fiber, its shrinkage factor in 100 ℃ of water is preferred more than 20%, is preferably 30～60% especially.By aliphatic polyester (B2) fiber that is spun into and the fiber that is spun into by above-mentioned polymer (A2), its shrinkage factor preferably differs more than 5%, especially preferably differs more than 10% the most widely-used 20～50% scope.

The composite fibre of caking property voluntarily of the present invention (IIa) be by fusing point more than 140 ℃, more than the fusion caloric receptivity 20J/g high crystalline aliphatic poly ester polymer (A2) with contain fusing point more than 130 ℃ high-melting-point composition (H) and the aliphatic polyester (B2) of fusing point two kinds of compositions of low melting point composition (S) of being 40～120 ℃ be composited, fibre composition (A2) keeps composition for intensity, and fibre composition (B2) is bonding (thermal welding) composition.

This is being characterised in that greatly of caking property fiber (IIa) voluntarily, and bonding composition (B2) uses fusing point to differ more than 20 ℃, preferably differs the block copolymer and/or the mixture of at least 2 kinds of crystallinity aliphatic polyesters more than 30 ℃.Make bonding and the temperature that high-melting-point is not bonding of the low melting point composition that constitutes this aliphatic polyester if this fiber (IIa) is heated to, then can obtain the relatively low goods of bounding point density or bonding strength, on the other hand, if be heated to the temperature that makes all the components fusion that constitutes aliphatic polyester (B2), then can obtain the highest bonding force and bounding point density.In addition, what take place during the melt spinning that caused by low melting point, lower glass transition temperatures composition is deadlocked, can be improved significantly by introduce the high-melting-point composition in aliphatic polyester (B2).Can also be by change constituting high-melting-point composition and the low melting point components in proportions of aliphatic polyester (B2), bonding force and the bounding point density of the coagulability when in wide region, changing melt spinning when adding heat bonding.Its result, the big advantage that fiber of the present invention (IIa) demonstrates are can make expeditiously, at the scope inner control and the adjusting bonding force of non-constant width.

Aliphatic polyester (B2) is for fusing point differs the block copolymer and/or the mixture of at least 2 kinds of crystallinity aliphatic polyesters more than 20 ℃, contains hard fat adoption ester (H) and fusing point low melting point aliphatic polyester composition (S) 90～10 weight %s and 10～90 weight %s that are 40～120 ℃ of fusing point more than 130 ℃ respectively.High-melting-point composition (H) is used to keep the heat resistance of composition (B2), it is deadlocked to take place when preventing melt spinning, and fusing point must be more than 130 ℃, and is preferred more than 140 ℃, preferred especially more than 150 ℃, most preferably more than 160 ℃.Low melting point composition (S) is to produce fusible composition through heating, and fusing point must be in 40～120 ℃ scope, is preferably 50～120 ℃, is preferably 60～120 ℃ especially.Each fusing point by changing high-melting-point composition (H) and low melting point composition (S) and mixing or the copolymerization ratio can change in wide region and heat tack temperature, bonding density and bonding strength, can select aptly according to application target.High-melting-point composition (H) in the aliphatic polyester (B2) is necessary for 9/1～1/9 scope with the weight ratio of low melting point composition (S), is preferably 8/2～2/8 scope, is preferably 7/3～3/7 especially.High-melting-point composition (H) in the aliphatic polyester (B2) and the fusion of low melting point composition (S) caloric receptivity more than the 3J/g, more than the preferred 5J/g, more preferably more than the 10J/g, are preferably about 10～30J/g respectively especially.Deadlocked viewpoint takes place when preventing spinning, and aliphatic polyester (B2) is preferably crystalline.

High-melting-point composition (H) in the aliphatic polyester (B2) must differ more than 20 ℃ with the fusing point of low melting point composition (S), preferably differs more than 30 ℃, especially preferably differs more than 40 ℃.For example, block copolymer or mixture that composition (S) combination of 80 ℃ of the composition (H) of 160 ℃ of fusing points and fusing points is formed, for example handling under 100 ℃, because of strongly bonded takes place in composition (S) fusion, and owing to exist high-melting-point composition (H) to make the whole not fusion maintenance of fibre composition (B2) shape to a certain degree.Therefore, can select to constitute composition (H) and the fusing point (S) and the ratio thereof of aliphatic polyester (B2) according to needed adhesion process temperature and pressure, bonding strength, heat resistance, serviceability temperature etc.

Crimpiness and voluntarily in the caking property composite fibre (IIa) voluntarily, aliphatic polyester (B2) are constituent (H) and (S) mixture and/or block copolymer.Mixed method is arbitrarily, can be common melting mixing, also can be to mix in solvent.The static mixer of cutting apart and converging that mixing arrangement can use mechanical stirring device or multistage to carry out the particle logistics repeatedly also can both merge use.In the melting mixing, also can make the reaction of twenty percent portions, form block copolymer.Just can not overreaction, all generate random copolymer (fusing point disappear, decrystallized).That is, use the dsc analysis molten mixture, investigate the fusing point and the fusion caloric receptivity of two kinds of compositions, wish to hold them in the preferred range.On the other hand, the block copolymer of two kinds of compositions can be by making obtaining with method that the low melting point aliphatic polyester (S) that for example has hydroxyl on molecular end carries out addition reaction (polymerization) for the annular lactone of high-melting-point composition (H) raw material of lactide or glycolide etc. under molten condition.In addition, also can make polyfunctional compound (chain extender) such as dicarboxylic acids halide such as dicarboxylic acids acid anhydrides, paraphthaloyl chlorides such as vulcabond, phthalic anhydride such as two isocyanic acid hexylene glycol esters for example and molecular end have the composition (H) of hydroxyl and (S) mixture reaction, make their in conjunction with and obtain block copolymer.For the resilience after improving heat-shrinkable and shrinking, the polymer of constituent (B) preferably has side chain or cross-linked structure.Can use for example trimellitic acid, glycerine, triisocyanate etc. to have the compound of 3 above functional groups.

For composition (H) and mixed stability ground (S) are carried out, wish both compatibility height.The improvement of both compatibilities can adopt preceding method to carry out.

In the composite fibre (IIa), polymer (A2) and the preferred cohesiveness height mutually of polymer (B2).Therefore, preferably both have common composition.For example, the high-melting-point composition (H) of special preferred polymers (B2) is identical component (a for example PLA) with polymer (A2).Similarly, also preferred both be approximate composition (for example PLA be the copolymer of main component) with the PLA.

Aliphatic polyester (B2) mainly constitutes by aliphatic polyester composition (H) with (S), also can contain submember (below the 50 weight %, particularly 30 weight % are following) other compositions, for example aromatic component, polyether components, Merlon composition, polyurethane composition, polyamide composition, organopolysiloxane composition.There is no particular limitation for the molecular weight of aliphatic polyester (B2), is preferably more than 50,000, is preferably 8～300,000 especially, is extensive use of 10～200,000 scope.

In the composite fibre (IIa), instantiation as the polyester that is suitable for low melting point composition (S), except polycaprolactone (about 59 ℃ of fusing point), beyond the poly-propiolactone aliphatic poly lactones such as (about 95 ℃ of fusing points), can also enumerate by ethylene glycol, propylene glycol, butanediol, hexylene glycol, ethohexadiol, diethylene glycol, more than one aliphatic diol class and succinic acid such as triethylene glycol, adipic acid, azelaic acid, decanedioic acid, the octane dicarboxylic acids, decane dicarboxylic acid etc. more than one aliphatic dicarboxylic acid combination and the polyester that obtains, for example polyethylene glycol succinate (about 102 ℃ of fusing point), polyethylene glycol adipate (about 49 ℃ of fusing point), polyethylene glycol suberate (about 65 ℃ of fusing point), polyethylene glycol azeleate (about 52 ℃ of fusing point), polyethylene glycol sebacate (about 75 ℃ of fusing point), poly butylene succinate (about 116 ℃ of fusing point), poly adipate succinic acid ester (about 72 ℃ of fusing point), polydiethylene glycol sebacate (about 66 ℃ of fusing point), poly-decanedioic acid hexylene glycol ester (about 74 ℃ of fusing point) and other homopolymers and be the block of composition or random copolymer and have crystalline polymer with them.By the bonded fiber structure that caking property composite fibre (IIa) voluntarily obtains, for example dye under the occasion of using as dress material, the fusing point of low melting point composition (S) is preferably more than 100 ℃, particularly preferably in more than 110 ℃.

Press usual way in the melt composite spinning respectively with polymer (A2) and polymer (B2) fusion, metering, make it compound in compound spinning head, spin from spinneret orifice, cooling, oil, stretch as required and heat treatment etc. makes molecularly oriented generate crystallization, makes composite fibre of the present invention (IIa).Similarly, polymer (A2) and polymer (B2) are used dissolution with solvents respectively, adopt methods such as wet type, dry type, dry-and wet-type to carry out composite spinning, also can obtain composite fibre of the present invention.The melt composite spinning method is because efficient is high but particularly preferred.Melt spinning can adopt winding speed 2000m/ to divide following low speed spinning, and can adopt winding speed is the high speed spinning that 2000～5000m/ divides, and also can adopt winding speed 5000m/ to divide above super high-speed spinning etc.In low speed spinning and the high speed spinning, can be the method for carrying out spinning and stretching process respectively, also can be spinning with the method for carrying out continuously and simultaneously of stretching etc.Usually, the stretching about 3～8 times is carried out in the low speed spinning, and high speed spinning carries out the stretching about 1.5～3 times, and super high-speed spinning does not need to stretch or carry out stretching following about 2 times.

Composite fibre (IIa) can form any forms such as the staple fibre of continuous multifilament yarn, continuous monofilament, cut-out, can adopt suitable the whole bag of tricks to make itself and other mixed with fibers, be used as with yarn, compile complex, other similar fiber structures of thing, fabric, nonwoven fabric, felt, paper, film etc.

Caking property composite fibre (IIa) is bonding voluntarily, in most cases fiber structure is heated or compresses and carry out.That heating can be used is xeothermic, damp and hot, infrared ray, high frequency and other methods.Usually, pressure is big more, and is easy more bonding at low temperatures.

Crimpiness composite fibre (IIa) occurs curling by heating voluntarily.That heating can be used is xeothermic, damp and hot, infrared ray, high frequency and other methods.Can regulate, control curling by change heating-up temperature, heat time heating time, tensity (tension force etc.).The appearance of curling can be carried out with long filament, tow, staple fibre, cotton, yarn, volume thing, fabric, nonwoven fabric, fibre web and other arbitrary shape attitudes.Under most occasions, under the condition of no tension force or low-tension, heat yarn, tow, cotton thread, fiber web, volume thing, fabric, nonwoven fabric etc. and occur curling.Before dyeing waits the arrangement manufacturing procedure, in arranging process, also occur mostly curling.Also can occur curling through the swelling contraction.For example, can be with the mixture of acetone, MEK or they and water as swelling agent.Also the aqueous dispersions that dilution such as other known water used in solvent can be formed is as swelling agent.

The composite fibre of crimpiness voluntarily of the present invention (IIa) has the cross sectional shape shown in for example Figure 1A～1G.Among the figure, 1 is low contractile element (A2), and 2 is high contractile element (B2), and they also can be changed mutually.Composition (A2) must be eccentric compound with composition (B2).Off-centre is meant two kinds of compositions position of centre of gravity difference separately, and eccentricity is high more, and the crimpiness of composite fibre is strong more.Figure 1A is the highest example of eccentricity, and Figure 1B is the low example of eccentricity.

There is no particular limitation for the compositely proportional (sectional area ratio) of the fibre composition (A2) in the crimpiness composite fibre (IIa) and fibre composition (B2) voluntarily, is preferably 10/1～1/10 scope, and more preferably 5/1～1/5, preferred especially 2/1～1/2 scope.It is 1/1 far away more that compositely proportional departs from, and crimpiness is weak more.

Fig. 4 A～4D is for illustrating the present invention fiber cross section figure of several examples of caking property composite fibre (IIa) voluntarily.Among the figure, 10 for intensity keeps with polymer (A2), and 11 is bonding composition (B2).Fig. 4 A is with one heart round compound, and Fig. 4 B is that the concentric type in triangle cross section is compound, and Fig. 4 C is the rotation symmetric form, and Fig. 4 D is a hollow round composite fibre with one heart.Among Fig. 4 D, 12 is the hollow part, also can replace to the third polymer.Must occupy at least a portion of fiber surface as the aliphatic polyester (B2) of bonding composition.Fig. 4 A, 4B, 4D are the example that composition (B2) occupies whole surface, and Fig. 4 C is the example that occupies part surface.The surperficial occupation rate of composition (B2) is high more, and bonding force is big more.There is no particular limitation for the compositely proportional (sectional area ratio) of the fibre composition (A2) in the caking property composite fibre (IIa) and fibre composition (B2) voluntarily, is 20/1～1/20, is preferably 10/1～1/10, and more preferably 5/1～1/5, be preferably 2/1～1/2 especially.Complex morphological must be that fibre composition (A2) is a concentric type with fibre composition (B2), and promptly center of gravity separately must be roughly consistent.

Identical with the occasion of composite fibre (I), there is no particular limitation for the cross sectional shape of composite fibre (IIa), can have different shapes such as circle, non-circular, polygon-shaped, compound leaf shape, hollow form.The fiber number of composite fibre (IIa) is selected arbitrarily according to application target equally, and the filament number that common dress material is used is about 0.1～50 dawn (d), especially, is preferably 0.5～30d, is extensive use of the scope of 1～20d.Nonwoven fabric, leather, material can use thinner or thicker fiber in using etc.Fiber of the present invention can adopt false twisting method and indentation method etc. that it is curled as required.Do not take place deadlockedly under the heating condition of optimum fiber in these curling operations, from this viewpoint, the minimum composition of fusing point in the aliphatic polyester (B2), its fusing point are preferably more than 60 ℃, and be preferred especially more than 80 ℃, most preferably more than 90 ℃.

In addition, identical with the occasion of composite fibre (I), composite fibre (IIa) also can contain various additives, can use separately or use with other mixed with fibers, is used to make yarn, braid, rope, volume thing, fabric, nonwoven fabric, paper, composite and other works.

Other preferred configuration of fiber (II) are alienable natural decomposition composite fibre (IIb), this composite fibre (IIb) be by the crystallinity aliphatic poly ester polymer (A2) of fusing point more than 140 ℃ with contain fusing point more than 140 ℃ crystallinity aliphatic polyester (H) and fusing point below 120 ℃ and glass transition temperature at the composite fibre of the block copolymer of the aliphatic polyester below 30 ℃ (S) or mixture (B2) formation, composition (A2) contains the above organopolysiloxane composition of 0.05 weight % with at least one side of composition (B2), make composition (A2) and composition (B2) compound in filament, so that in fiber cross section, composition (B2) is separated at least 2 parts with composition (A2), and two kinds of compositions (A2) and the part surface that (B2) forms fiber.

In the alienable composite fibre (IIb), the composition that polymer (A2) is the crystallinity height, heat-shrinkable is low.As preferred polymer (A2), can enumerate above-mentioned crystallinity homopolymers and a small amount of (for example below the 30 weight % to destroy its crystalline degree copolymerization and/or mixing hardly, below the preferred 20 weight %, preferred especially 10 weight % are following) second kind of composition and the third composition and the copolymer or the mixture that form.The intensity and the stable on heating viewpoint of the goods that make from fiber (IIb), polymer (A2) fusion recepts the caloric more than the preferred 20J/g, more preferably more than the 30J/g, more than the preferred especially 40J/g.From the viewpoint of practicality, the fusing point of polymer (A2) is necessary more than 140 ℃, and is preferred more than 150 ℃, preferred especially more than 160 ℃, most preferably more than 170 ℃.

Aliphatic polyester (B2) can be to make the crystallinity aliphatic polyester segment (H of fusing point more than 140 ℃, below be sometimes referred to as rigid chain segment) with fusing point below 120 ℃ and glass transition temperature at the aliphatic polyester segment (S below 30 ℃, below be sometimes referred to as soft segment) block copolymer that combines also can be an above-mentioned crystallinity aliphatic polyester (H) and the mixture of above-mentioned aliphatic polyester (S).Because be to constitute by composition (H) and (S), very big contraction takes place through heating in aliphatic polyester (B2), its result, polyester (A2) separates easily with polyester (B2), and divided fiber attenuates.In order to reach high purpose of shrinking, preferred high melting point polyester composition (H) is firm, and its fusing point must be more than 140 ℃, and is preferred more than 150 ℃, preferred especially more than 160 ℃, most preferably more than 170 ℃.On the other hand, low-melting point polyester composition (S) is preferably submissive more, and thermal contraction is big more, under the occasion of crystalline polymer, fusing point is necessary below 120 ℃, and is preferred below 100 ℃, preferred especially below 90 ℃, most preferably below 80 ℃ or amorphism (amorphism).For example, when handling in 100 ℃ of water, if the fusing point of low-melting point polyester composition (S) below 100 ℃, then fibre composition (B2) is strong shrinks.But the fusing point of high melting point polyester composition (H) is more than 140 ℃, and fibre composition (B2) shrinks but not fusion.Similarly, in order to realize big purpose of shrinking, the glass transition temperature of low-melting point polyester composition (S) is preferred below 20 ℃, and is preferred especially below 0 ℃.Low-melting point polyester composition (S) is under the occasion of amorphism fully, fusing point is regarded as identical with glass transition temperature.

Aliphatic polyester (B2) in the Splittable conjugate fiber (IIb), as being specially adapted to its low-melting point polyester composition (S), fusing point below 120 ℃ and glass transition temperature at the example of the polyester below 0 ℃, except polycaprolactone, can enumerate polyethylene glycol succinate, polyethylene glycol adipate, polyethylene glycol sebacate, polyethylene glycol azeleate, poly-capric acid glycol ester, the poly-succinic propylene glycol ester, PPA, poly-decanedioic acid propylene glycol ester, poly-azelaic acid propylene glycol ester, poly-capric acid propylene glycol ester, poly butylene succinate, poly adipate succinic acid ester, polydiethylene glycol sebacate, polytetramethylene azelaate, poly-capric acid butanediol ester, poly-succinic hexylene glycol ester, poly-adipic acid hexylene glycol ester, poly-decanedioic acid hexylene glycol ester, poly-azelaic acid hexylene glycol ester, the aliphatic aklylene glycol that has by the straight or branched alkylidene of carbon number about 2～20 of poly-capric acid hexylene glycol ester etc. is (random and block) copolymer of composition with the polyester of the aliphatic dicarboxylic acid generation of carbon number about 4～22 and with them.In addition, the polyester ether that is also preferably combined by aklylene glycol oligomer such as diethylene glycol, triethylene glycol, ethylene propylene glycol and aliphatic dicarboxylic acid is as low-melting point polyester composition (S).

Usually, it is crystalline that homopolymers mostly is, and by with its copolymerization more than 2 kinds (random or block), low-melting point polyester composition (S) or degree of crystallinity reduced, and perhaps becomes decrystallized.In addition, fibre composition (B2) uses under the occasion of composition (H) and mixture (S), the compatibility height of the block copolymer of crystallinity high melting point polyester and low-melting point polyester and high melting point polyester (H) can mix, easily and equably therefore especially preferably as low-melting point polyester (S).There is no particular limitation for the molecular weight of the low-melting point polyester composition (S) in the aliphatic polyester (B2), under the occasion of block copolymer, the molecular weight of soft segment (S) for example more is preferably 1000～150,000, more preferably 2000～100,000, be preferably 5000～50,000 especially, under the occasion of blend polymer, the many preferences of molecular weight of low-melting point polyester (S) are as 10,000～300,000, more preferably 20,000～250,000, be preferably 50,000～200,000 especially.Have again,, also can add plasticizer etc. in order to improve the shrinkage of fibre composition (B2).

In the aliphatic polyester (B2) as the instantiation of the high melting point polyester composition (H) of crystallinity aliphatic polyester as mentioned above.In order to make this part firmer, it must be high crystalline, in order to keep crystallinity, homopolymers most preferably, when coming the occasion of modification, also preferably suppress the amount of second kind of composition, for example below the preferred 20 weight % of the amount of second kind of composition by copolymerization or mixing, below the preferred especially 10 weight %, most preferably below the 5 weight %.Use as fibre composition (B2) under the occasion of blend polymer, block copolymerization the high melting point polyester of low-melting point polyester and the Combination height of low-melting point polyester composition (S), preferably as high melting point polyester composition (H).There is no particular limitation for the molecular weight of high melting point polyester composition (H), under the occasion of block copolymer, the molecular weight of rigid chain segment (H) can be for example 5000～200,000, majority more preferably 8000～100,000, preferred especially 10,000～50,000, under the occasion of blend polymer, the molecular weight of high melting point polyester (H) is preferably 50,000～300,000, majority more preferably 80,000～250,000, majority is preferably 100,000～200,000 especially.

Aliphatic polyester (B2) be high melting point polyester (H) with the occasion of the mixture of low-melting point polyester (S) under, there is no particular limitation for admixture, preferably makes two kinds of compositions fine and mix equably.For fine and mix equably, preferred compatibility height mutually, the gradation composition that a preferred side or both sides mix with the opposing party, with for example at the most about 50 weight %, preferred 5～30 weight %, the more preferably copolymer of the ratio block copolymerization of 10～20 weight %.In addition, in order to improve the Combination of two kinds of compositions, also can add composition or intermixture that the third less important composition for example has the surfactant function.The weight ratio of high melting point polyester (H) and low-melting point polyester (S), according to the characteristic of employed each composition and difference, for intensity, elastic modelling quantity (spring rate), heat resistance and the heat-shrinkable etc. that obtain preferred fiber, this ratio is 1/9～9/1, be preferably 2/8～8/2, more preferably 3/7～7/3.The crystallinity of high melting point polyester (H) and fusing point are high more firm more, and the crystallinity of low-melting point polyester (L) and fusing point are low more submissive more, also have effect on a small quantity even only have respectively.

There is no particular limitation for the molecular weight of blend polymer (B2), in order to carry out the melting mixing spinning with polymer (A2), wish composition (A2) and (B2) melt viscosity about equally, the whole weight average molecular weight of blend polymer (B2) is preferably near the molecular weight of polymer (A2).That is, the weight average molecular weight of blend polymer (B2) is preferably more than 50,000, and more preferably 70,000～300,000, be preferably 80,000～200,000 scope especially.

Blend polymer (B2) is high melting point polyester (H) is mixed with low-melting point polyester (S) and to obtain.There is no particular limitation for mixed method, for example the particle of the two can be mixed by a certain percentage, extrudes mixing roll or other mixing rolls etc. with screw extruder or twin-screw and carry out melting mixing.Similarly, can be respectively the two of fusion be mechanically mixed with agitating device, also can mix with static mixer.Static mixer is to carry out cutting apart and converging of polymer fluid repeatedly with flowing to guiding device, also can merge with mechanical stirring device and use.If adopt fusion method to mix, then high melting point polyester (H) generates copolymer with low-melting point polyester (S) reaction.Under the occasion of fusing point reduction that the copolymer that must prevent to generate causes, heat resistance deterioration etc., melting mixing is as far as possible in the short time, for example 30 minutes with interior, especially, preferably carried out with interior at 20 minutes.Similarly, react, also can carry out esterification and wait end-blocking the polymer molecule end in order to prevent two kinds of compositions.In addition, also two kinds of compositions can be dissolved in the solvent and mix.

Under the occasion of aliphatic polyester (B2) for block copolymer that rigid chain segment (H) and soft segment (S) are combined, in conjunction with mode there is no particular limitation, can be common chemical bond.Can be for example ehter bond, amido link, urethane bond, urea key and other chemical bonds.For example, in the low melting point aliphatic polyester that soft segment is used, can make lactide or glycolide and terminal pet reaction (polymerization), form rigid chain segment with hydroxyl.In addition, the soft segment that all has hydroxyl on dicarboxylic acids acid anhydrides or carboxylic acid halides and the end is connected with pet reaction with polyester and rigid chain segment.Under these occasions, joint is an ester bond.In addition, also can make the reaction of vulcabond and terminal hydroxyl, be connected with urethane bond.The weight ratio of rigid chain segment (H) and soft segment (S), according to the characteristic of employed each composition and difference, for the intensity that obtains preferred fiber, elastic modelling quantity, heat resistance, heat-shrinkable etc., this ratio is 2/8～8/2, be preferably 3/7～7/3, be preferably 4/6～6/4 scope especially.Rigid chain segment (H) is firm more, and perhaps soft segment is submissive more, even amount separately also has effect less.

There is no particular limitation for the weight average molecular weight of block copolymer (B2), is more than 50,000 under most occasions, and more preferably 80,000～300,000, be preferably 100,000～200,000 scope especially.

First reason that composite fibre of the present invention (IIb) can be easier to cut apart (peeling off) is, the thermal shrinkage force of above-mentioned polymer (A2) and polymer (B2) or the difference of shrinkage factor are big.The boiling water shrinkage of polymer (A2) is preferred below 20%, and is preferred especially below 15%, most preferably below 10%.Similarly, the shrinkage factor of polymer (B2) is preferred more than 20%, and is preferred especially more than 30%, most preferably more than 40%.Polymer (A2) preferably differs more than 10% with the shrinkage factor of polymer (B2), especially preferably differs more than 20%, most preferably differs more than 30%.Usually, the low-melting point polyester composition (S) in the polymer (B2) is many more, and its shrinkage factor is big more.According to above explanation, selective polymer (A2) and polymer (B2) can be realized the poor of sufficient shrinkage factor easily.

Second reason that composite fibre of the present invention (IIb) can more easily be cut apart is that because polymer (A2) contains organopolysiloxane composition with a side or the both sides of polymer (B2), therefore mutual cohesiveness is low.Organopolysiloxane has side chain alkyl and/or aryl, can enumerate for example dimethyl silicone polymer, polymethy ethylsiloxane, poly-di-ethyl siloxane, PSI, poly-diphenyl siloxane etc., most preferably dimethyl silicone polymer.Composition (A2) or (B2) in organopolysiloxane composition many more, the cohesiveness of composition (A2) and composition (B2) is low more, easy more peeling off.Composition (A2) and (B2) content of at least one side's organopolysiloxane composition be more than the 0.05 weight %, preferred above 0.1 weight %, more preferably 0.3～8 weight % is preferably 0.5～5 weight % especially.Especially, the preferred content of organopolysiloxane composition in composition (B2) is more than the content in the composition (A2), or only is used for composition (B2).

Make composition (A2) or (B2) in contain organopolysiloxane method copolymerization method and mixing method are arranged.Copolymerization method can be to make the organopolysiloxane and the aliphatic polyester that have hydroxyl on the end etc. make raw material, for example lactide or glycolide react (polymerization), also can be to mix with aliphatic polyester that end has a hydroxyl, make for example dicarboxylic acids acid anhydrides, dicarboxylic acids carboxylic acid halides, di-isocyanate reaction, thereby make the two combination.For example, can with etc. the prepolymer of mole vulcabond and polysiloxanes terminal hydroxyl reaction (the having isocyanate group) that generate be mixed into and make its reaction in the aliphatic polyester with hydroxyl.

Mixing method is that organopolysiloxane is mixed into method in the aliphatic polyester, but the two lacks mutual compatibility, evenly mixes quite difficulty.A method improving compatibility is to use surfactant.Additive method is the method for the block copolymer of use aliphatic polyester and organopolysiloxane.The manufacture method of the block copolymer of aliphatic polyester and organopolysiloxane evenly is mixed in the aliphatic polyester block copolymer of making in addition than being easier to and being the most practical as mentioned above.Make this block copolymer in addition,, can use common apparatus and method, for example powerful agitating device, ultrasonic unit, surfactant etc. and be to be relatively easy to because aequum is few.In this aliphatic polyester that should mix with aliphatic polyester and the block copolymer of organopolysiloxane, the content of organopolysiloxane composition is 5～95 weight %, is preferably 10～90 weight %, more preferably 20～80 weight %.This block copolymer also can be used as the dispersant (surfactant) when making organopolysiloxane disperse (mixing) in aliphatic polyester, and applied range is particularly useful to the present invention.

In the cross section of composite fibre (IIb), must be polymer (B2) be separated at least 2 parts (below be sometimes referred to as layer) with polymer (A2), and two kinds of compositions occupy the part surface of fiber.Adopt this composite construction, composite fibre (IIb) can be divided into some, can obtain the fiber of the little special cross-section of fiber number simultaneously.The number of plies of the polymer (A2) in the filament is many more, and the fiber of acquisition is thin more, specific area is big more.Cutting apart number must be more than 2, and the most widely-used about 3～20.Cut apart number and be about 3～10 composite fibre and be applicable to coat, jacket, women underwear etc., cut apart number and be 4～20 composite fibre as superfine fiber, be applicable to VHD braided fabric, nonwoven fabric, manually imitative chamois leather, artificial leather, filter cloth, cloth for wiping or dusting etc.

Be applicable to the cross-sectional configurations of composite fibre of the present invention (IIb) shown in Fig. 3 A～3I.Among the figure, 7 is polymer (A2), and 8 is polymer (B2), and 9 is the hollow part.Fig. 3 A is 3 Splittable examples of 3 layers of parallel type.Parallel type is the structure of instigating two kinds of composition alternate configurations.Fig. 3 B is for being divided into polymer (A2) with the radiate layer of polymer (B2) 4 layers example.Radial pattern be meant side's composition for example the form of polymer (B2) be radial.Fig. 3 C is 9 layers of radial pattern composite fibre, Fig. 3 D is 9 layers of multiple parallel composite fiber, Fig. 3 E is petal-like 9 layers of radial pattern composite fibre, the composite fibre of Fig. 3 F for radial pattern and multiple parallel type are combined, Fig. 3 G is non-circular radial pattern composite fibre, Fig. 3 H is the multiple parallel composite fiber of distortion, and Fig. 3 I is a hollow radial pattern composite fibre.Except Fig. 3 A～3I,, can also have diversified compound according to the present invention.Can also compound the third composition except that polymer (A2) and polymer (B2).For example, the third polymer can be configured in the hollow part of Fig. 3 I.One side's composition occupies the composite construction on the whole surface of fiber, and the sort of core-sheath shown in for example Fig. 3 J, 3K and island type structure cannot be used for composite fibre (IIb).

There is no particular limitation than (sectional area ratio) for polymer (A2) and polymer (B2) compound, can select arbitrarily according to purpose.Under most occasions, compound ratio is preferably 20/1～1/5 scope, is preferably 10/1～1/2 scope especially.That is, in most cases, low contractile element (A2) proportion is more suitable greater than the ratio of high contractile element (B2), compoundly most preferably is 10/1～1/1 than (A2)/(B2).

The cross sectional shape of composite fibre (IIb) can be selected arbitrarily.Filament number (before cutting apart) is selected arbitrarily according to application target too, is generally for 0.5～50 dawn, especially, preferably uses for 1～30 dawn, especially preferably uses the scope at 1.5～20 dawn.

By the method for polymer (A2) and polymer (B2) manufacturing composite fibre (IIb), identical with the occasion of composite fibre (I).

Composite fibre of the present invention (IIb) can be any form of the staple fibre etc. of continuous filament yarn, monofilament, multifilament, cut-out according to application target.In the composite fibre (IIb), use the silicon composition in a large number, the mutual cohesiveness between the composition is weakened especially, and only adopting stretches will occur peeling off or chap.If heating or make its swelling is then further peeled off and is cut apart.When fissility is weak, remove heat or swelling, can use false twisting as required, rub, mechanical means such as dabbing.Also can use with dissolution with solvents and remove the method that polymer (B2) is cut apart, but the preferred not method of peeling off of bodies lost weight.Usually, in the fiber manufacturing or be processed in the process such as braided fabric and will peel off the potential degree that is suppressed at, preferably after forming braided fabric etc., for example in dyeing and finishing process, peel off completely and cut apart.This is the reason that becomes fault owing to the cut-outs such as friction that superfine fibre, superfine fiber are easy to manufactured and manufacturing procedure.

Another preferred configuration of fiber (II) is fiber (IIc), this fiber comprises that (A2) is by fusing point more than 140 ℃ and the fibre composition that constitutes of the crystallinity aliphatic poly ester polymer more than the fusion caloric receptivity 20J/g, and (B2) be by being main component with the aliphatic polyester, be actually noncrystalline, glass transition temperature at the crystallinity segment of the soft segment below 40 ℃ (S) and the aliphatic polyester of fusing point more than 110 ℃ and/or have a fibre composition that the block copolymer of rigid chain segment (H) be combined into that the segment of urethane bond constitutes constitutes.

Fiber (IIc) can be fibre composition (A2) is engaged in filament with (B2) and to form composite fibre, also can be that the fiber (A2) that makes each composition mixes with (B2) and forms compound silk.Based on the heat-shrinkable of fibre composition (B2), fiber (IIc) has good bulkiness, flexibility and feel.Make the eccentric composite fibre that engages of fibre composition (A2) and (B2) give play to better crimpiness voluntarily, the retractility of curling fiber is also good.

In the fiber (IIc), polymer (A2) is the little composition of heat-shrinkable.As preferred polymer (A2), can enumerate the crystallinity homopolymers and with destroy hardly its crystalline degree copolymerization and/or mix a small amount of (for example below the 40 weight %, below the preferred 30 weight %, more preferably 20 weight % are following) copolymer or the mixture of second kind of composition and the third composition.From the viewpoint of crimpiness, intensity, heat resistance or the feel of fiber, polymer (A2) must be more than the 20J/g, more than the preferred 30J/g, more than the preferred especially 40J/g at the fusion caloric receptivity.From the viewpoint of practicality, the fusing point of polymer (A2) is necessary more than 140 ℃, and is preferred more than 150 ℃, more preferably more than 160 ℃, preferred especially more than 165 ℃.

Polymer (B2) is actually the block copolymer of amorphism (amorphism), be by being that the soft segment (S) and the specific rigid chain segment (H) of main component constitutes at the aliphatic polyester below 40 ℃ with glass transition temperature, wherein also comprise copolymerization or be mixed with a small amount of (below the 50 weight %, below the preferred 40 weight %, more preferably 30 weight % are following) other compositions person.Herein, segment refers to the part of polymer molecular chain, is also referred to as block (block).

Adopt above-mentioned special construction, polymer (B2) demonstrates so-called elastomeric elastic behavior, from the function admirable of the replying state that stretched, if be spun into fiber, then demonstrates high heat-shrinkable.In order to demonstrate high heat-shrinkable, the glass transition temperature of soft segment (S) is necessary below 40 ℃, and is preferred below 20 ℃, more preferably below 0 ℃.Make under the occasion of composite fibre, the glass transition temperature of soft segment is preferred below 20 ℃, and is preferred especially below 0 ℃.Glass transition temperature can be measured with DSC shown in Figure 7, and more accurate with the main maximum temperature of disperseing of the loss of the mechanics in the viscoelastic mensuration (for example measuring under 1～60Hz) (tan δ).Be actually amorphism (amorphism) and be meant below the dissolving and heat absorbing amount 5J/g that obtains by the DSC curve, below the preferred 3J/g.

As the example that is suitable for soft segment (S), can enumerate by copolymerization or mixing and make crystallinity disappearance or in fact decrystallized aliphatic polyester.For crystallinity being disappeared or in fact becoming decrystallized, under the occasion of two kinds of compositions, copolymerization (weight) ratio is preferably about 1/1, that is, and and about 2/1～1/2.

As the example of the glass transition temperature that is suitable for soft segment (S), can enumerate polycaprolactone at the aliphatic polyester below 0 ℃, polyethylene glycol succinate, polyethylene glycol adipate, polyethylene glycol sebacate, polyethylene glycol azeleate, poly-capric acid glycol ester, the poly-succinic propylene glycol ester, PPA, poly-decanedioic acid propylene glycol ester, poly-azelaic acid propylene glycol ester, poly-capric acid propylene glycol ester, poly butylene succinate, poly adipate succinic acid ester, polydiethylene glycol sebacate, polytetramethylene azelaate, poly-capric acid butanediol ester, poly-succinic hexylene glycol ester, poly-adipic acid hexylene glycol ester, poly-decanedioic acid hexylene glycol ester, poly-azelaic acid hexylene glycol ester, poly-capric acid hexylene glycol ester etc. has the polyester of the straight or branched alkylidene of carbon number about 2～20.Except above-mentioned, the polyether ester that is combined by aklylene glycol oligomer such as diethylene glycol, triethylene glycol, ethylene propylene glycol and aliphatic dicarboxylic acid is also preferably as the soft segment composition.The homopolymers of these polyester generally is crystalline, therefore it must be mixed more than 2 kinds and copolymerization (random and/or block copolymerization), and in fact crystallinity is disappeared.There is no particular limitation for the molecular weight of soft segment, for example is 1000～200,000, and more preferably 1500～150,000, preferred especially 2000～100,000, most preferably use about 5000～50,000.

The soft segment (S) of polymer (B2), with the aliphatic polyester of amorphism (amorphism) in fact as main component.As mentioned above, the amorphism aliphatic polyester can easily obtain by several aliphatic polyesters or its are made raw material random copolymerization or block copolymerization.For example, if the raw material about 1/3～3/1 of polyethylene glycol adipate and PPA, particularly 1/2～2/1 mixed in molar ratio are come polymerization, then can obtain low-crystalline～non-crystalline aliphatic polyester.In addition, for example, if being 1/1 mixture 40 weight portions and lactide 60 weight portions, the weight ratio that makes molecular end have the polyethylene glycol adipate of hydroxyl and poly-decanedioic acid propylene glycol ester carries out melt polymerization, then can obtain two kinds of polymer that block copolymer mixes of PLA/polyethylene glycol adipate, PLA/poly-decanedioic acid propylene glycol ester, in this mixed polymer, polyethylene glycol adipate segment and poly-decanedioic acid propylene glycol ester segment partly form non-crystalline soft segment, and polylactic acid chain segment forms crystalline rigid chain segment.That is, decrystallized can the employing of soft segment easily carried out methods such as several composition random copolymerizations, block copolymerization or mixing.Under the occasion of 2 compositions, the weight ratio of copolymerization or mixing is preferably 1/2～2/1.Whether non-crystalline, can recepting the caloric by the crystallization fusion that DSC measures, whether not enough 5J/g, particularly not enough 3J/g judge.

In the rigid chain segment (H) of polymer (B2), can use two types and this combination of two types, amount to 3 kinds of rigid chain segments.

First type of rigid chain segment (H) is fusing point more than 110 ℃, preferred more than 120 ℃, the more preferably crystallinity aliphatic polyester more than 140 ℃.The instantiation of this dystectic crystallinity aliphatic polyester as mentioned above.In order to keep this high-melting-point, preferred homopolymers carries out under the occasion of modification with copolymer etc., the amount of second kind of composition of control, and for example the amount with second kind of composition is controlled at below the 20 weight %, more preferably below the 10 weight %, below the preferred especially 5 weight %.There is no particular limitation for the molecular weight of crystallinity rigid chain segment, and for the high-melting-point sufficient crystallising, molecular weight is preferably 5000～200,000, and more preferably 10,000～100,000, be preferably 10,000～50,000 especially.

Second type of the rigid chain segment (H) of polymer (B2) is the aliphatic polyester with urethane bond, for example can make isocyanates, and the above-mentioned aliphatic polyester that preferred vulcabond and terminal soft segment with hydroxyl are used reacts and forms.As the example of vulcabond, can use aliphatic and aromatic diisocyanates such as two isocyanic acid butanediol esters, two isocyanic acid hexylene glycol esters, two isocyanic acid ethohexadiol esters, the inferior phenyl ester of two isocyanic acids, two isocyanic acid benzal esters, Xylene Diisocyanate, two isocyanic acid benzhydryl esters.Further add glycol such as ethylene glycol as chain extender, propylene glycol, butanediol, neopentyl glycol, hexylene glycol, use superfluous slightly vulcabond as required, can increase the molecular weight of rigid chain segment or the number of urethane bond, make rigid chain segment firmer.But if a large amount of the use as the diamines (with high density) of chain extender introduced the urea key, then fusing point becomes too high (for example 230 ℃ with first-class), and it is difficult that melt spinning becomes, and is not preferred therefore.Should illustrate that if use aromatic diisocyanate, then elastic performance is good, but easy to change, biological degradability is variation also, and on the other hand, aliphatic diisocyanate has opposite tendency, can select according to purpose and purposes.Should illustrate that a small amount of in chain extender or isocyanates (for example 5 moles % below) compound more than use 3 functional groups also can be introduced side chain or cross-linked structure in polymer.

The third type of rigid chain segment (H) is above-mentioned 2 types combination, for example, can be to make vulcabond and crystallinity rigid chain segment with the terminal hydroxyl reaction with polyester of the terminal hydroxyl of polyester and amorphism soft segment, make the two in conjunction with and obtain.Under this occasion, around polymer crystallization, produce the urethane bond part that can form hydrogen bond, rigid chain segment is strengthened.

There is no particular limitation for the rigid chain segment (H) of polymer (B2) and the ratio of soft segment (S) and elastic performance, can wait aptly according to the purpose of the character of used rigid chain segment and soft segment and goods and purposes and select.Under the occasion of compound silk, usually, rigid chain segment is many more, and fiber is firm more, and heat resistance is good more, and soft segment is many more, and the flexibility of fiber is good more.Fiber (B2) can be made in the elastic performance scope of non-constant width, has extremely strong elastic fiber like that from so-called elastic spandex fiber (elastic yarn), the fiber that after in spinning, stretching and heat treatment, making to a certain degree molecularly oriented fixing, shrinks through heat treatment and with various shrinkage factors or convergent force again.But, usually, purpose of the present invention, in spinning, stretching and heat treatment, make to a certain degree molecularly oriented fix, when in 100 ℃ water, handling, shrinkage factor is preferably 15～80%, be preferably 20～70% especially, the most widely-used about 30～60%.Therefore, under the occasion of compound silk, the content of the rigid chain segment (H) in the polymer (B2) is preferably 10～90 weight %, and more preferably 20～80 weight % are preferably 30～70 weight % especially.

Under the occasion of composite fibre, the rigid chain segment (H) of polymer (B2) and the weight ratio of soft segment (S) are preferably 20/80～80/20, and more preferably 25/75～75/25, be preferably 30/70～70/30 especially.Usually, the structure of rigid chain segment is firm more, and the glass transition temperature that has soft segment is low, be non-crystalline, that the warm-up movement free degree is high a kind of compliant structure, and the elastic performance of fibre composition (B2) is good more, and the crimpiness of composite fibre is high more.In addition, even firmer rigid chain segment also has effect on a small quantity, similarly, even glass transition temperature is also high in a small amount of effect of the soft segment below 0 ℃.

There is no particular limitation for the molecular weight of block copolymer (B2), is preferably 50,000～300,000, is preferably 80,000～200,000 especially.

For manufacture method, processing method or the fiber (A2) of compound silk (IIc) and (B2) boiling water shrinkage, cross sectional shape, fiber number, mixing ratio and other aspects, in addition for manufacture method, cross sectional shape, the fiber number of composite fibre (IIc), poor, compound other aspects when of curl processing or composition (A2) and percent thermal shrinkage (B2), identical with the occasion of compound silk (I) and composite fibre (I), therefore omit explanation to them.

Present inventors find, in the aliphatic polyester that relatively is subject to basic hydrolysis, further cooperate hydrophilic compounds, make itself and the fusing point crystallinity aliphatic polyester compound tense in filament more than 140 ℃, can obtain the composite fibre that adopts chemical treatment to cut apart easily.The present invention also provides a kind of composite fibre (III), this composite fibre be by the crystallinity aliphatic poly ester polymer of (A3) fusing point more than 140 ℃ with, (B3) by aliphatic polyester be selected from the composition that at least a compound 1～50 weight % in the following compounds mixes and in filament, be composited, and in cross section, composition (B3) is separated at least 2 parts with polymer (A3); Wherein, said compound be selected from polyethers, this polyethers of alkylidene with carbon number 2～4 derivative, have sulfonic organic compound, have sulfate group organic compound, have carboxyl organic compound, have phosphate organic compound, have the organic compound of amino and/or amide groups.

Composite fibre of the present invention (III) is that the crystallinity aliphatic poly ester polymer (A3) of fusing point more than 140 ℃ formed with the aliphatic polyester system: compositions (B3) compound (joint) that is combined with specific hydrophilic composition.Because the aqueous alkali of composition (B3) is water-disintegrable greater than polymer (A3), so this composite fibre is handled through aqueous alkali and is cut apart easily.

The aqueous alkali of polymer (A3) is water-disintegrable relatively little, as preferred instantiation, can enumerate poly (l-lactic acid) (175 ℃ of fusing points), poly-D-lactic acid (175 ℃ of fusing points), poly 3-hydroxy butyrate (180 ℃ of fusing points), polyglycolic acid (230 ℃ of the fusing points) homopolymers of etc.ing, and copolymerization and/or mix the copolymer or the mixture of other compositions on a small quantity in them.Usually, crystallinity and fusing point reduce slowly in the block copolymerization, below the preferred 50 weight % of the ratio of copolymer composition, are preferably 1～40 weight % especially, are preferably 1～30 weight % under most occasions.In the random copolymer, being changed significantly of crystallinity and fusing point, so the ratio of copolymer composition is preferably 0.5～20 weight %, is preferably 1～10 weight % especially.

In order to suppress polymer (A3) by basic hydrolysis, can be by mixing or copolymerization introducing hydrophobic ingredient.As hydrophobic ingredient, can enumerate have carbon number be more than 10, in particular for the aliphatic acid of the alkyl more than 15 or fatty alcohol, their ester or acid amides, paraffin class, polyethylene and derivative thereof, organopolysiloxane (for example dimethyl silicone polymer) and derivative thereof etc.There is no particular limitation for the content of hydrophobic ingredient in the polymer (A3), is 0.1～20 weight % under most occasions, especially, is preferably about 0.5～10 weight %.There is no particular limitation for the molecular weight of polymer (A3), be preferably more than 50,000 under most occasions, and more preferably 70,000～300,000, be preferably 80,000～200,000 especially.

The composition that polymer (A3) is the crystallinity height, hydrolysis rate is low, further preferred heat resistance height, the composition that heat-shrinkable is low.From intensity and heat resistance viewpoint, the fusing point of polymer (A3) is more than 140 ℃, and is preferred more than 150 ℃, more preferably more than 160 ℃, preferred especially more than 170 ℃.From the viewpoint of practicality, the soakage the during fusion of polymer (A3) is preferably more than 20J/g, more preferably more than the 30J/g, more than the preferred especially 40J/g.

Composition (B3) mixes for crystallinity or non-crystalline aliphatic polyester and specific hydrophilic compounds, said specific hydrophilic compounds be selected from polyethers, this polyethers of alkylidene with carbon number 2～4 derivative, have sulfonic organic compound, have sulfate group organic compound, have carboxyl organic compound, have phosphate organic compound, have at least a in the organic compound of amino and/or amide groups.By using this hydrophilic composition, make composition (B3) become very responsive to the aqueous solution of water and alkali metal (sodium, potassium, lithium, calcium, magnesium etc.) compound, be hydrolyzed easily, its result, (III) cut apart with composite fibre of the present invention, perhaps merge to use other means, for example mechanical means or utilize under the occasion of dividing method of chemical swelling are cut apart and are become easy.Therefore, in the aqueous solution of for example sodium carbonate (carbonated soda) 3 weight % in the weak base aqueous solution of fibrous composition (B3), decomposition rate under 98～100 ℃, it is the weight slip in the unit interval, be more than 1.5 times of weight slip of polymer (A3), more preferably more than 2 times, preferred especially more than 5 times, preferred more especially more than 10 times, be extensive use of about 5～200 times usually.The hydrophilic compounds that mixes in the preferred composition (B3) can with the aliphatic polyester melting mixing, and preferred composition (B3) can carry out melt composite spinning.

First group of hydrophilic compounds is polyethers and the derivative thereof with alkylidene of carbon number 2～4.Instantiation as polyethers, can enumerate polyethylene glycol, polypropylene glycol, polytetramethylene glycol and their copolymer, example as its derivative, can enumerate the reactant of these polyethers (also comprising oligomer) and other compositions, for example, the nonionic surfactants, polyethers and other polymer that combine with ester bond or ehter bond of polyethers and composition copolymer of aliphatic polyester (particularly block copolymer) etc. particularly with alkyl or alkaryl.For example, the block copolymer of polyethylene glycol and aliphatic polyester, with the affinity height of the matrix components aliphatic polyester of composition (B3) be preferred.Especially, if the aliphatic polyester segment in this block copolymer is identical with the matrix components aliphatic polyester, then mutual affinity is best, can mix easily and stably.For example, the matrix polymer that makes composition (B3) is PLA or its copolymer, and with the combination as hydrophilic compounds of the block copolymer of polyethylene glycol and PLA, mutual affinity is high, is preferred.Similarly, making matrix polymer is poly butylene succinate, and making hydrophilic compounds is that the combination of polyethylene glycol/poly butylene succinate block copolymer also is preferred.As the example of the manufacture method of the block copolymer of polyethers/aliphatic polyester, can enumerate the polymer raw that makes aliphatic polyester and have the method for the polyether reactant of hydroxyl, a method that makes epoxides (oxirane etc.) and terminal aliphatic polyester carry out addition reaction (polymerization) with hydroxyl with terminal.The hydrophily of polytetramethylene glycol is not necessarily high, in most cases, is mixed into the compound with other polar groups and obtains good hydrophily.Have the polymer of these polyether components or non-ionic surface active agent etc., with the melt fluidity height, have for example compound of polar group of other groups, also can improve its thermoplasticity.

Second group of hydrophilic compounds be for to have the organic compound of sulfonic group (particularly alkali metal salt) or sulfate group, can enumerate the sulfuric ester surfactants such as (sodium salts) of the thermoplastic polymer that for example makes vinyl sulfonic acid, sulfonated phenylethylene (sodium salt), sodium methallyl sulfonate, 2-acrylamide 2-methyl propane sulfonic acid sodium etc. have the polymerization of vinyl monomer of sulfonic group (sodium salt etc.) or copolymerization and generate, sodium alkyl benzene sulfonate, various higher alcohols.Should illustrate, these sulfonic compounds or sulfuric acid ester, under the occasion that has, thermoplasticity is not necessarily high, in most cases, mixes to obtain good melt fluidity with polyethers such as above-mentioned non-ionic surface active agent or polyethylene glycol.Especially, because the excellent heat resistance of sulfonic compound, so practicality is the highest.

The 3rd group of hydrophilic compounds is for having the organic compound of carboxyl (particularly alkali metal salts or ammonium salt), except various organic carboxyl acids, polybasic carboxylic acid etc., can enumerate polymer of vinyl monomer and copolymer that acrylic acid, methacrylic acid, maleic acid, fumaric acid etc. have carboxyl.Even under the low occasion of thermoplasticity, mix with aforesaid non-ionic surface active agent or polyethylene glycol etc., also can obtain good melt fluidity.

The 4th group of hydrophilic compounds is the compound (particularly alkali metal salt and ammonium salt) with phosphate, can enumerate the sodium salt and the sylvite of the monoesters, diester etc. of phosphoric acid, they mix with aforesaid non-ionic surface active agent or polyethylene glycol etc., can obtain good melt fluidity.

The 5th group of hydrophilic compounds is the hydrophily height of the compound with amino and/or amide groups, particularly quaternary ammonium salt.As this compound with amino or amide groups, the polymer with amide groups, polymine, the polyvinylpyrrolidone that can enumerate acid amides that alkylamine for example, polyamines, amine and carboxylic acid reaction generate, generate by the acrylamide copolymerization, make that oxirane etc. and amine carry out that addition reaction generates have an amino polyethers etc.

The content of the hydrophilic compounds in the composition (B3) is 1～50 weight %, under most occasions, is preferably about 3～30 weight % the scope of preferred especially 5～20 weight %.

The main component of composition (B3) (more than the 50 weight %) is an aliphatic polyester, and is preferred easily by the polyester of basic hydrolysis.Therefore, preferred crystallinity is low, and for example following, the following polyester of preferred especially 20J/g of caloric receptivity 30J/g during fusion also can be an amorphism.In addition, the aliphatic polyester that constitutes composition (B3) preferably by copolymerization and/or mixing contain more than the 10 weight %, the particularly fusing point more than the 20 weight % below 120 ℃, particularly the aliphatic polyester composition below 100 ℃, preferred especially fusing point below 120 ℃, the particularly aliphatic polyester below 100 ℃.Similarly, the glass transition temperature of this aliphatic polyester is preferred below 30 ℃, more preferably below 0 ℃.The aliphatic polyester that fusing point and glass transition temperature are low, its decomposition rate in the aqueous alkali below 100 ℃ is big.

There is no particular limitation for the molecular weight of the aliphatic polyester of composition (B3), in order to carry out melt composite spinning with polymer (A3), wish melt viscosity almost with polymer (A3) about equally or approximate, the weight average molecular weight of composition in its entirety also preferably approaches the molecular weight of polymer (A3).That is, the mean molecule quantity of composition (B3) is preferably 70,000～300,000, most preferably 8～200,000 scope especially preferably more than 50,000.

Composition (B3) can make aliphatic polyester mix with hydrophilic compounds and obtain.There is no particular limitation for mixed method, for example particle or the powder of the two can be mixed by a certain percentage, extrudes mixing roll or other kneading devices etc. with screw extruder or twin-screw and carry out melting mixing.Similarly, also the two of other fusion can be mixed with mechanical stirring device, also can mix with static mixer.Static mixer is by with flowing to the device of cutting apart Yu converging that guiding device carries out polymer fluid repeatedly, also can merge with mechanical stirring device and use.In addition, under the occasion that does not hinder the aliphatic polyester polymerization, also can in polymerization process, mix.In most cases, composition (B3) is decomposed in manufacturing procedure fully to be removed, and does not remain in the end article.Therefore, its painted or dyeing firmness etc. is a problem hardly.But the product of hydrolysis for example adopts preferably that activated sludge process is decomposed it fully.As above-mentioned hydrophilic compounds, be easy to select to be actually the compound of Biodegradable.

In the cross section of composite fibre (III), composition (B3) must be separated into polymer (A3) at least 2 parts (below be sometimes referred to as layer).Utilize this composite construction, remove composition (B3), composite fibre (III) can be divided into some, obtain the fiber of the little special cross-section of fiber number by decomposition.The number of plies of the polymer (A3) in the filament is many more, and the fiber of acquisition is thin more, specific area is big more.Cutting apart number must be preferably about 3～50 more than 2, especially, and the most widely-used about 4～30.Cut apart number and be about 3～10 fiber and be applicable to coat, jacket, chemise etc., cut apart number and be 4～30 fiber, be applicable to VHD braided fabric, nonwoven fabric, manually imitative chamois leather, artificial leather, filter cloth, cloth for wiping or dusting etc. as superfine fiber.

Cross section, fiber number and the method for making of composite fibre (III) is identical with the occasion of composite fibre (IIb).Composite fibre (III) can have the various cross-sectional configuration shown in for example Fig. 3 A～3K, also can be core skin structure or island structure shown in Fig. 3 J and 3K.

There is no particular limitation than (sectional area ratio) for polymer (A3) and composition (B3) compound, can select arbitrarily according to purpose.Under most occasions, compound ratio is preferably 20/1～1/2, is preferably 10/1～1/1 scope especially.That is, the shared ratio of polymer (A3) is greater than composition (B3) proportion, but the loss in weight of preferred bases hydrolysis is little.

Composite fibre of the present invention (III) can be a form arbitrarily such as continuous filament yarn, monofilament, multifilament, cut-out staple fibre, spinning silk according to application target.

Composite fibre (III), for weaken composition (A3) and (B3) between mutual cohesiveness, also can resemble and contain organopolysiloxane the composite fibre (IIb).

The alkali treatment that is used to cut apart can be carried out under normal temperature or heating with the aqueous solution of NaOH, potassium hydroxide, sodium carbonate and other alkali compoundss.The kind of alkali cpd, concentration, pH value, processing time etc. are arbitrarily, but in most cases, the pH value is preferably more than 7.5, more preferably more than 8, particularly preferably in more than 9.But if the pH value is too high, then polymer (A3) also is decomposed, therefore, and the preferred condition of selecting to decompose or damage hardly polymer (A3).

On the other hand, when decomposability or fissility are weak, except heating with make its swelling, also can use false twisting as required, rub, mechanical means such as dabbing.That is, except through alkali treatment carry out cut apart, can also adopt other chemical method or mechanical means to cut apart.The method of peeling off of employing mechanical means etc. is compared with the dividing method of removing composition (B3) through basic hydrolysis fully, has the few advantage of the loss in weight.Usually, preferably in the process of braided fabric etc. is processed in fiber manufacturing neutralization, suppress to peel off and cut apart, after forming braided fabric etc., in dyeing and finishing process for example, make it peel off fully and cut apart.This is the cut-outs such as friction that are easy to manufactured or manufacturing procedure owing to superfine fibre, superfine fiber, causes trouble.

Utilize the shape retention of the highly shrinkable and the hard fat adoption ester of low melting point aliphatic polyester, with the low melting point aliphatic polyester as the core silk, hard fat adoption ester is made the composite fibre that they are bonded together as epidermis, can give play to good highly shrinkable, by with this composite fibre and other natural decomposition mixed with fibers, can obtain all good natural decomposition fibres such as bulkiness, flexibility and feel.In addition, the invention provides a kind of fiber assembly that mixes by core-sheath composite fibre (X) and other natural decomposition fibers (Y) different with it, it be with, said core-sheath composite fibre be with the crystallinity aliphatic poly ester polymer (A4) of fusing point more than 140 ℃ as epidermis, with contain fusing point more than the 10 weight % than the polymer (C) of the low aliphatic poly ester polymer (B4) more than 20 ℃ of this polymer (A4) as the core silk.

Fiber assembly be meant yarn, staple fibre, cotton thread, tow, fiber web, volume thing, fabric, nonwoven fabric and with they similar works.

Be applicable to the crystallinity aliphatic polyester (A4) of fusing point more than 140 ℃ of epidermis, can enumerate poly (l-lactic acid) (about 175 ℃ of fusing point), poly-D-lactic acid (about 175 ℃ of fusing point), poly 3-hydroxy butyrate (about 180 ℃ of fusing point), polyglycolic acid homopolymers such as (about 230 ℃ of fusing points) and be that main component is (more than the 50 weight % as the example with them, particularly more than the 70 weight %), copolymerization therein and/or mix a small amount of (below the 50 weight %, particularly 30 weight % are following) polymer of other compositions, and also fusing point is more than 140 ℃.As other compositions, for example can enumerate aliphatic polyester or their raw material, aromatic polyester, polyethers, Merlon, polyamide, polyureas, polyurethane, organopolysiloxane etc. as mentioned above such as the polyester that generates by aliphatic dicarboxylic acids such as aliphatic diol such as ethylene glycol, ethohexadiol and succinic acid, decane dicarboxylic acids or polycaprolactone.

Be the polymer (A4) of heat resistance composition, its fusing point must be more than 140 ℃, and is preferred more than 150 ℃, more preferably more than 160 ℃.Caloric receptivity during its fusion is preferably more than the 20J/g, more preferably 20～55J/g.As polymer (A4), preferably use the homopolymers of aliphatic polyester, but in order to improve heat-resisting shrinkage and to improve dyeability and other performances, the preferred polymer that suitably mixes with other compositions with copolymerization that uses.There is no particular limitation for the molecular weight of polymer (A4), from the viewpoint of practicality, be preferably more than 50,000, and more preferably 8～300,000, be preferably 10～250,000 especially.

On the other hand, the core silk is to be made of aliphatic poly ester polymer (C), it contain 10 weight % above, fusing point is than the low aliphatic poly ester polymer (B4) more than 20 ℃ of polymer (A4).That is, the core silk is to form by low melting point aliphatic polyester (B4) itself (100%) or by the polymeric blends that contains (B4) more than 10% or block and/or random copolymer.

Like this, be used for the polymer of core silk and epidermis, can be the block of homopolymers, several mixture of polymers and several polymer and/or random copolymer any.For example, the random copolymer of the manufacturing raw material of 90/10 (weight ratio) mixture of poly (l-lactic acid)/poly adipate succinic acid ester, the block copolymer of poly (l-lactic acid)/poly adipate succinic acid ester and these polymer, the low melting point composition poly adipate succinic acid ester that all contains 10 weight % can be used as core silk polymer (C).

One of above-mentioned composite fibre (X) is characterised in that greatly epidermis is made of dystectic heat resistance composition, and the core silk is the high contractile element that contains the low melting point composition.For example, make the softening or fusion of low melting point aliphatic polyester composition and hard fat adoption ester (epidermis composition A) is softening as yet or the state of fusion if temperature is heated to, then composite fibre shrinks strongly, and the whole shape that keeps softening or fusion.With low melting point aliphatic polyester composition (B4) 100% ground or be used for as main component under the occasion of core silk, and under occasion that makes its block copolymerization and the occasion with its mixing, this effect is (fusing point is obvious) significantly.Under the occasion of the polymer (C) of a small amount of random copolymerization low melting point composition (B4), based on the low melting point composition, make fusing point become not obvious, can fully confirm the effect that its shrinkage factor increases.In any occasion, the compositely proportional of core silk (C) is big more, and the amount of the low melting point composition (B4) in the core silk (C) is many more, and then the heat-shrinkable of composite fibre (X) is strong more.By selecting these factors aptly, can realize the heat shrink temperature and the shrinkage factor of wide region, make it satisfy various application targets.

Should illustrate; usually; when the low melting point aliphatic polyester carries out melt spinning; bonding mutually (deadlocked) easily takes place in fiber; it is extremely difficult to make the high efficiency that adopts melt spinning make fiber, and composite fibre (X) also can be subjected to the protection of high-melting-point polymer epidermis even the low melting point composition is used for the core silk; therefore, carry out melt spinning easily.Have again; usually; the low melting point composition is extremely responsive to aqueous alkali etc.; be decomposed easily and extremely fast; composite fibre (X) also can be subjected to the decomposition rate protection of high-melting-point epidermis more slowly, therefore even use the low melting point composition; the alkali decomposition rate tends to slower, has the advantage of carrying out the processing of alkali decrement easily.This advantage is effective especially under a kind of occasion, that is, with other fiber blended formation braided fabrics after carry out alkali decrement processing, for example about 5～30% removing the polymer of fiber surface, thereby provide good flexibility to goods.For the processing of alkali decrement, preferred especially core silk and epidermis are concentric, that is, in cross section, the center of gravity of the two is roughly consistent, and epidermal thickness is roughly certain.

The first group of polyester that is suitable for as low melting point composition (B4) is with the polyester of the low melting point aliphatic polyester of fusing point below 120 ℃ as main component, as its instantiation, can enumerate for example polycaprolactone (about 59 ℃ of fusing point), poly-propiolactone aliphatic poly lactones such as (about 95 ℃ of fusing points); By ethylene glycol, propylene glycol, butanediol, hexylene glycol, ethohexadiol, diethylene glycol, aliphatic diol classes such as triethylene glycol more than one and succinic acid, adipic acid, azelaic acid, decanedioic acid, the octane dicarboxylic acids, more than one combinations of aliphatic dicarboxylic acids such as decane dicarboxylic acid and the aliphatic polyester of fusing point below 120 ℃ that obtain, for example polyethylene glycol succinate (about 102 ℃ of fusing point), polyethylene glycol adipate (about 49 ℃ of fusing point), polyethylene glycol suberate (about 65 ℃ of fusing point), polyethylene glycol azeleate (about 52 ℃ of fusing point), polyethylene glycol sebacate (about 75 ℃ of fusing point), poly butylene succinate (about 116 ℃ of fusing point), poly adipate succinic acid ester (about 72 ℃ of fusing point), polydiethylene glycol sebacate (about 66 ℃ of fusing point), poly-decanedioic acid hexylene glycol ester homopolymers such as (about 74 ℃ of fusing points) and be the block or the random copolymer of main component with these homopolymers; And be main component (more than the 50 weight %) with these low melting point aliphatic polyesters, mix therein or other compositions that copolymerization 50 weight % are following for example high melting point polyester or aromatic polyester raw material and the polyester that forms etc.

Be suitable for second group of polyester as low melting point composition (B4), be as main component (more than the 50 weight %) with the hard fat adoption ester of fusing point more than 140 ℃, copolymerization therein and/or mix other compositions makes fusing point or crystallinity fully reduce the polyester of (for example more than 20 ℃).For example, if with D-lactic acid with 3 moles more than the %, particularly 4 moles of ratio random copolymerizations more than the % then can easily obtain fusing point than the low copolymer more than 20 ℃ of poly (l-lactic acid) (homopolymers) in poly (l-lactic acid).Except the copolymerization of optical isomer, can also enumerate the combination of different types of hydroxycarboxylic acids such as lactic acid/glycollic acid, lactic acid/butyric acid, butyric acid/valeric acid and incorporate into aliphatic lactones such as caprolactone, butyrolactone in these combinations and copolymer of forming etc.

The combination of aforesaid hard fat adoption ester and the low melting point aliphatic polyester that generates by aliphatic dicarboxylic acid and aliphatic diol, their block copolymer for example, if more than the content of the low melting point aliphatic polyester 10 weight %, then be preferably used as core silk composition (C) into composite fibre (X).For example, 70/30 block copolymer of poly (l-lactic acid)-poly adipate succinic acid ester contains 30 weight % low melting point compositions, preferably as the core silk composition (C) of composite fibre (X).About the copolymerization mode, the feature of random copolymerization is to reduce fusing point and crystallinity effectively, and the feature of block copolymerization is to introduce the low melting point composition to destroy crystallinity and stable on heating degree hardly, is useful especially.Similarly, in high-melting-point aliphatic polyesters such as PLA or their raw material, also can a spot of aromatic polyester raw material of copolymerization, perhaps also can mixed with little amount other composition.

Low melting point aliphatic polyester composition (B4) in the core silk composition polymer (C), its content is big more, and the heat-shrinkable of composite fibre (X) is high more.The content of low melting point aliphatic polyester composition (B4) is more than the 10 weight %, more than the preferred 20 weight %, and 25～100 weight % more preferably.Have again, in order to improve shrinkage or resilience, core silk and/or epidermis polymer also can contain a spot of (carrying out in the scope of melt polymerization and melt spinning) branched structure or cross-linked structure.Therefore, also can be on a small quantity (for example 5 moles below the %, particularly 3 moles of % are following) use the polyester raw material with 3 above functional groups, for example trimellitic acid, glycerine etc.In addition, contain for example 5～70 weight % in the core silk composition polymer (C), particularly about 10～60 weight % with the same or analogous high-melting-point composition of epidermis composition (A4), both improved the cohesiveness of core silk and epidermis, appropriate heat settability is provided again, causing contraction effectively through heating then, is very suitable.

The fusing point of low melting point composition (B4) must be lower more than 20 ℃ than the fusing point of epidermis composition (A4), and this fusing point preferably differs more than 30 ℃, more preferably differs 40～120 ℃.If for example making the fusing point of epidermis composition (A4) is 175 ℃, the fusing point that makes low melting point composition (B4) is about 100 ℃, then can obtain sufficient shrinkage factor under 90～130 ℃ damp and hot or dry heat condition.Should illustrate that in the manufacturing process of composite fibre, the molecularly oriented that the preferred drawn of the polymer of core silk composition (C) produces is temporarily fixed (heat setting), through the heat shrink operation its liberation shunk then.That is, preferred core silk composition is crystalline, perhaps contains the above composition of glass transition temperature normal temperature.Usually, from elastic viewpoint, to a certain degree containing the composition and the low a little crystallinity of glass transition temperature low (normal temperature following), i.e. fusion caloric receptivity is about 5～40J/g, particularly the composition about 10～30J/g is preferably as core silk composition (C).Should illustrate, the following normal temperature of glass transition temperature major part of above-mentioned low melting point aliphatic polyester, majority is below 0 ℃, and the glass transition temperature of PLA is high especially, is 58 ℃.Therefore, fusing point is 40～120 ℃, fusing point is 60～120 ℃ a aliphatic polyester especially, its homopolymers is also preferably as core silk composition (C), also preferably mixes in homopolymers and/or the composition of (random and/or block) copolymerization a small amount of other (high-melting-points etc.) and the polyester that forms.

There is no particular limitation for the molecular weight of core silk composition (C), is more than 50,000, and more preferably 8～300,000, the most widely-used 10～250,000 scope.

Polymer (A4) and (C) with aliphatic polyester as main component, also can contain as submember (below the 50 weight %, particularly 30 weight % are following) other compositions, for example aromatic component, polyether components, Merlon composition, polyurethane composition, polyamide composition, organopolysiloxane composition etc.

Composite fibre (X) can adopt aforesaid common composite spinning method to make.There is no particular limitation for compositely proportional (sectional area ratio), and the ratio of epidermis/core silk is generally 5/95～80/20, is preferably 10/90～70/30, is preferably 15/85～60/40 especially.The compound ratio of epidermis is 2～10% such hours, and epidermis becomes as thin as a wafer, and shrinkage is extremely strong, after the strong contraction of core silk, it is concavo-convex that epidermis presents the snake abdomen shape of camera (カ メ ラ), can obtain the feel of unique smooth (coefficient of friction is low), can be used for special volume thing or fabric etc.

The shrinkage factor of composite fibre (X) can extensively and freely change by employed polymer, compositely proportional, the degree of orientation (stretching ratio), heat treatment etc.In order to obtain highly shrinkable, do not heat-treat after the stretching or under lower temperature, carry out.Composite fibre (X) zero load down, when in 100 ℃ water, handling 10 minutes, its shrinkage factor is preferably more than 15%, more preferably more than 20%, is preferably about 25～70% especially.

Composite fibre (X) can be made form arbitrarily such as continuous multifilament yarn, continuous monofilament, cut-out staple fibre, adopt suitable various means to make its and other mixed with fibers, complex, other similar fiber assemblies of being used to yarn, volume thing, fabric, nonwoven fabric, felt, paper, film etc. are fiber structure.

There is no particular limitation except natural decomposition for the other side's fiber that mixes, the fiber that percent thermal shrinkage is low, and for example the preferred less than 15% of the shrinkage factor of 100 ℃ of water, preferred below 12% especially most preferably (comprises through adding the fiber of thermal stretching) below 10%.In the natural fabric, preferred cotton, fiber crops, wool, the thin,tough silk etc. of using, preferred regenerated cellulose and aliphatic poly ester fiber in the artificial fibre.For example, particularly preferred instantiation is a composite fibre (X) and be the mixture of the polyester fiber (Y) of main component with the PLA, wherein, composite fibre (X) is that the polyester that will be main component is that the polymer made of PLA block copolymerization that low melting point aliphatic polyester about 100 ℃ is measured about with 20～80 weight % is as the core silk as epidermis (polymer (A4)), with fusing point with the PLA.There is no particular limitation for the method and structure that mixes, representative is the combination of long filament/long filament, long filament/staple fibre, staple fibre/staple fibre, and implementing preferred instantiation of the present invention is that so-called spinning mixes fibre, the mixed fibre of stretching, doubling and twisted filament, false twisting mixes fibre, mixing fibre web, blending, bag core silk, the mixed goods that uses them, mixing volume thing, hybrid nonwoven cloth etc.The percent thermal shrinkage of the percent thermal shrinkage of composite fibre (X) and blending objects fiber (Y) differs big more, the bulkiness or the flexibility of the fibre that obtains are good more, shrinkage factor preferably differs about 5～70%, especially preferably uses about 10～50% the most widely-used about 15～40%.

As mentioned above, using composite fibre (X) and the fiber structure of other fibers (Y) to carry out under the occasion of alkali decrement processing to mixing, the alkali resistance of the epidermis composition polymer of composite fibre (X) is preferably with the alkali resistance roughly the same (1/2～2/1) of the other side's fiber (Y) that mixes or on it.Because the alkali reduction rate is generally 5～30%, particularly about 10～25%, be that the compositely proportional of epidermis is more than 10%, and is preferred more than 20% under certain occasion therefore making the alkali decrement, more preferably 30～50%.

Be used to make composite fibre (X) to shrink, provide the heating of bulkiness or flexibility can use xeothermic, damp and hot, infrared ray and other methods to fiber assembly.By changing heating-up temperature, programming rate, heat time heating time, tensity (tension force etc.), can regulate and control contraction.Can under long filament, tow, staple fibre, cotton thread, yarn, volume thing, fabric, nonwoven fabric, fiber web and other arbitrary shape attitudes, carry out heat shrink.Under most occasions, make yarn, tow, cotton thread, fiber web, volume thing, fabric, nonwoven fabric etc. under the condition of no tension force or low-tension, carry out heat shrink, the length of two kinds of fibers is differed to more than 3%, particularly differ to more than 5%, most occasions differ about 750%, so just bulkiness or flexibility can occur.Under the occasion of cloth, generally before arrangement manufacturing procedures such as refining, dyeing or in arranging process, carry out shrink process.

Fig. 5 A～5C illustrates the example of the cross section of the composite fibre (X) that is used for the present invention.Among the figure, 13 is epidermis, and 14 is the core silk.Fig. 5 A is concentric round composite fibre, and Fig. 5 B is the composite fibre of non-circular (triangle), and Fig. 5 C is a hollow round composite fibre with one heart.Among Fig. 5 C, 15 is the hollow part, also can replace with the polymer identical with epidermis, also can replace with the third polymer.Concentric type be epidermis with core silk center of gravity separately roughly (in fact) consistent, also carry out composite spinning easily, be preferred.Except Fig. 5 A～5C, for example also have, with non-circular core silk be combined to the fiber that forms in the circular fiber, with the core silk of circle be combined to the fiber that forms in the non-circular fiber, fiber that several core silk concentric arrangement are formed etc. is various is concentric core-sheath, applicable to the present invention.Make the structure of the eccentric configuration of core silk and epidermis also go for the present invention, but from the easiness of processing of alkali decrement or composite spinning, preferred especially concentric type.Should illustrate that it is long-pending that epidermis occupies the fiber all surfaces, the core silk is exposing surface not.

Fig. 6 A～6C be example go out embodiment of the present invention, composite fibre (X) is mixed the sectional view of the silk (compound silk) that forms with other fibers (Y), among the figure, 16 be composite fibre (X), 17 for other fibers (Y), 18 be other other fibers.Fig. 6 A is the composite fibre (X) and 9 compound silks that other circular cross-section fibers (Y) roughly are uniformly mixed to form of 9 circular cross-sections, Fig. 6 B be make circular cross-section composite fibre (X) in the centre, other fibers (Y) of noncircular cross section dispose the core-sheath compound silk that forms around, Fig. 6 C is that the composite fibre (X) of circular cross-section mixes the compound silk that forms side by side with other fibers (Y) of 2 kinds of noncircular cross sections.

The mixing ratio of composite fibre (X) and other fibers (Y) does not have special fiber, can adjust according to purpose, is preferably 5/95～95/5 (weight ratio) usually, and more preferably 10/90～90/10, be preferably 20/80～80/20 especially.

There is no particular limitation for the cross sectional shape of composite fibre (X) and other fibers (Y), can be circular, non-circular, polygon-shaped, compound leaf shape, hollow form etc.The fiber number of composite fibre (X) and other fibers (Y) is selected arbitrarily according to application target equally, and dress material is about 0.1～50 dawn (d) with the filament number of fiber usually, is preferably 0.5～30d especially, is extensive use of 1～20d.The fiber that nonwoven fabric, leather, material are used etc. can use thinner or thicker fiber.Composite fibre (X) can adopt false twisting method or indentation method etc. that it is curled as required.Under the heating in these curling operations, optimum fiber is not deadlocked, from this viewpoint, is difficult to deadlockedly owing to be subjected to being used for the composite fibre (X) of high-melting-point epidermis protection of the present invention, is preferred yet.

Can in each fiber that constitutes compound silk of the present invention and composite fibre, cooperate various pigment, dyestuff, colouring agent, water-repelling agent, water absorbing agent, fire retardant, stabilizing agent, antioxidant, ultra-violet absorber, metallic, inorganic compound particles, crystallization nucleating agent, lubricant, plasticizer, antiseptic, spices and other additives.

Compound silk of the present invention and composite fibre can use separately or use with other mixed with fibers, can be used to make yarn, braid, rope, volume thing, fabric, nonwoven fabric, paper, composite and other works.Under the occasion of using with other mixed with fibers, if with natural decomposition mixed with fibers uses such as natural organic fiber such as cotton, wool, thin,tough silk, aliphatic poly ester fiber, then can obtain to be entirely the goods of natural decomposition, thereby be particularly preferred.

Fiber of the present invention is a natural decomposition, low in the pollution of the environment, and goods such as good volume thing such as flexibility, bulkiness, elasticity, heat resistance, retractility, fabric, nonwoven fabric can be provided, be highly suitable for various dress materials, industrial materials, industry material, household supplies etc.Because fiber of the present invention carries out melt spinning easily, make the efficient height, cost is low.Have again, because the crimpiness fiber can easily be realized curling of various intensity voluntarily, has the extremely wide advantage of easy use, range of application, and voluntarily the caking property fiber can be in very wide temperature range the intensity with hope bonding, therefore have the extremely wide and bonded goods heat resistance advantages of higher that obtains of easy use, range of application.In addition, Splittable fiber of the present invention can easily be cut apart, and natural decomposition and extremely soft high-performance fiber goods can be provided.Usually, the aliphatic poly ester fiber not only decomposes under natural environment, and the thermal discharge in when burning also more employed synthetic fiber were few than past, burnt easily.Especially the material acid of PLA is to obtain through fermentation method from agricultural product; owing to be included in the middle of the natural material circulating system; do not increase Carbon Dioxide in Air gas, see it is most preferred as the aliphatic polyester of main component from the viewpoint of environmental protection with PLA.

Below based on embodiment the present invention is described, but the present invention is not subjected to the qualification of these embodiment.Should illustrate that in following examples, %, part all are benchmark with weight if not otherwise specified.

Among the present invention, the molecular weight of aliphatic polyester is 0.1% chloroformic solution with the gpc analysis sample, the weight average molecular weight of removing the macromolecule component of the composition of molecular weight below 1000.

The crimp extension rate of composite fibre is to make the sample long filament form the tow of about 1000 (950～1050) dawn, long 50cm, after in boiling water, handling 10 minutes under the uncharge condition, carry out centrifugal dehydration, 23 ℃, humidity 65% indoor, in zero load down air dry more than 24 hours, measure respectively then apply the 0.5g load after 1 minute length L 1 and apply the length L 2 of 500g load after 1 minute, calculate with formula [(L2-L1)/L1] * 100 (%).

The percent thermal shrinkage of fiber is to make the sample long filament form the tow of about 1000 dawn, the about 50cm of length, in 100 ℃ warm water, handled 10 minutes down zero load, 22 ℃, the indoor air dry of humidity 65% 24 hours, by the length L 3 before dried length L 4 and the heat treatment, calculate with formula [(L3-L4)/L3] * 100 (%).The length of fiber is mensuration after per 1 dawn silk applies 10mg load 1 minute.

Embodiment 1

With molecular weight is 8000, two terminal 0.1 part of mixing of antioxidant Irganox1010 for 3 parts of the polyethylene glycol of hydroxyl (PEG), 98 parts of L-lactides, tin octoate 100ppm, Ciba-Geigy company, in nitrogen atmosphere, under 190 ℃, polymerization 12 minutes is stirred in fusion in double screw extruder, after the cooling section, in 140 ℃ nitrogen atmosphere, handled (solid phase) 4 hours, obtain the block copolymer P1 of PLA and PEG.The molecular weight of polymer P 1 is 153000, and the PEG component content is about 3%, and fusing point is 174 ℃, and fully the fusion caloric receptivity during oriented crystalline is 55J/g.Afterwards,, similarly carry out, obtain polymer P 2 with polymer P 1 except that using by 95.5 parts of L-lactides, 2.5 parts of mixtures that constitute of D-lactide as lactide.The molecular weight of polymer P 2 is 158000, and fusing point is 163 ℃, and the fusion caloric receptivity is 27J/g.

Polymer P 1 and polymer P 2 are used 220 ℃ screw extruder fusion respectively, feed 2 polymer supply units of compound spinning head.Two polymer are combined into as shown in Figure 1 parallel type (compound ratio 1/1), spin from diameter 0.25mm, 225 ℃ spinneret orifice, in air, cool off, while the speed of dividing with 1500m/ that oils is reeled, under 80 ℃, be stretched to 4.5 times, obtain the drawn yarn F1 of 70 dawn/24 threads.The intensity of drawn yarn F1 is 4.6g/d, and degree of stretching is 29%, and the crimp extension rate after occurring curling is 226%, and is good.

In order to compare, except that not using PEG, similarly carry out preparation PLA homopolymers P3 with polymer P 1.The molecular weight of polymer P 3 is 162000, and fusing point is 175 ℃, and the fusion caloric receptivity is 55J/g.Having, similarly carry out with polymer P 1, is 95 parts but making PEG is 6 parts, make the L-lactide, makes polymer P 4.The molecular weight of polymer P 4 is 155000, and the PEG that contains as copolymer composition is about 6%, and fusing point is 173 ℃, and the fusion caloric receptivity is 55J/g.Use polymer P 3 and P4, below similarly carry out, obtain drawn yarn F2 (comparative example) with drawn yarn F1.The intensity of drawn yarn F2 is 4.8g/d, and degree of stretching is 31%, and the crimp extension rate after occur curling is 19%, crimpiness extremely a little less than.

Embodiment 2

Replace PEG for 30 parts with the poly butylene succinate that molecular weight is 127000, end has hydroxyl, in addition,, obtain polymer P 5 by similarly carrying out with the manufacturing of the polymer P 1 of embodiment 1.The molecular weight of polymer P 5 is 129000, and fusing point is 162 ℃, and the fusion caloric receptivity is 35J/g.

Similarly carry out with polymer P 1, but replace PEG, replace the L-lactide for 2.52 parts with 88.5 parts of L-lactides and D-lactide, acquisition polymer P 6 with 10 parts of molecular weight is 12700, end has hydroxyl poly butylene succinates.The molecular weight of polymer P 6 is 134000, and fusing point is 151 ℃, and the fusion caloric receptivity is 26J/g.

Similarly carry out with the drawn yarn F1 of embodiment 1, but obtain drawn yarn F3 with polymer P 1 and polymer P 5.The intensity of drawn yarn F3 is 4.7g/d, and degree of stretching is 28%, and the crimp extension rate is 223%, and crimpiness is good.

Similarly carry out with the drawn yarn F1 of embodiment 1, but be to use polymer P 1 and polymer P 6 to obtain drawn yarn F4.The intensity of drawn yarn F4 is 4.6J/g, and degree of stretching is 29%, and the crimp extension rate is 236%, and crimpiness is good.

Embodiment 3

Carry out similarly to Example 1, make the block copolymer P1 of PLA and PEG.Screw extruder fusion with 230 ℃ of polymer P 1 usefulness, spin from 225 ℃, the spinneret orifice of diameter 0.2mm, in air, cool off, while the speed coiling that oils and divide with 1500m/, under 80 ℃, be stretched to 4.5 times, under tension, under 110 ℃, heat-treat, obtain the drawn yarn A1 of 40 dawn/12 threads.The intensity of drawn yarn A1 is 4.5g/d, and degree of stretching is 29%, and boiling water shrinkage is 12%.

Have again, carry out similarly to Example 1, make polymer P 2.With the screw extruder fusion of 220 ℃ of polymer P 2 usefulness, spin from 225 ℃, the spinneret orifice of diameter 0.2mm, in air, cool off, while the speed coiling that oils and divide with 1500m/, under 80 ℃,, do not heat-treat, obtain the drawn yarn B1 of 60 dawn/12 threads with 4.5 times of stretchings.The intensity of drawn yarn B1 is 4.4g/d, and degree of stretching is 33%, and boiling water shrinkage is 27%.

With each 1 of drawn yarn A1 and drawn yarn B1, mix through air nozzle, obtain to make the two mixed uniformly combined yarn MY1 in the silk cross section.Combined yarn MY1 is used for warp thread with the twist yarn that 600 times/m twists, with twisting count is that the twist yarn of 30T/m is used for weft yarn, make 2/1 drillipg, after the refining, under lax state, with 120 ℃ of xeothermic heat-treating 15 minutes, carry out handling in 10 minutes (decrement processing) with 80 ℃ caustic soda 0.5% aqueous solution again.Then, washing adds 0.2% soft finishing agent, heat-treats under 135 ℃ of anxieties, obtains fabric MF1.

In order to compare, carry out similarly to Example 1, make the PLA homopolymers P3 of 175 ℃ of fusing points, fusion caloric receptivity 55J/g and fusing point and be 174 ℃, fusion caloric receptivity and be the PLA of 55J/g/PEG block copolymer P4.Use polymer P 3, similarly carry out, obtain the drawn yarn A2 of 40 dawn/12 threads with drawn yarn A1.The intensity of drawn yarn A2 is 4.6g/d, and degree of stretching is 30%, and boiling water shrinkage is 12%.Use polymer P 4, similarly carry out, obtain the drawn yarn B2 of 60 dawn/12 threads with drawn yarn A1.The intensity of drawn yarn B2 is 4.5g/d, and degree of stretching is 29%, and boiling water shrinkage is 15%.Drawn yarn A2 and each 1 of drawn yarn B2 is evenly mixed fine with air nozzle, obtain combined yarn MY2.Use combined yarn MY2 to carry out the processing of alkali decrement with caustic soda 0.6%, the processing time is 30 minutes, in addition, similarly carries out with fabric MF1, obtains fabric MF2.The characteristic of fabric MF1 and fabric MF2 is shown in Table 1.

Table 1

Fabric	Flexibility	Bulkiness	Feel	Remarks
					MF1	Well	Well	Well	The present invention
MF2	Bad slightly	Bad slightly	Bad slightly	Comparative example

Embodiment 4

Carry out similarly to Example 2, make the block copolymer P5 and the polymer P 6 of PLA and poly butylene succinate.

Use polymer P 5, make spinning and stretch and carry out continuously, adopt the mode of spinning drawing-off, making spinning speed is the 4000m/ branch, draft temperature is 80 ℃, and stretching ratio is 1.6 times, does not heat-treat, in addition, the drawn yarn B1 with embodiment 3 similarly carries out acquisition drawn yarn B3.The intensity of drawn yarn B3 is 4.7g/d, and degree of stretching is 33%, and boiling water shrinkage is 38%.

Use the polymer P 1 of embodiment 3, heat-treat under 120 ℃ the back that stretches, and in addition, similarly carries out with drawn yarn B3, obtains drawn yarn A3.The intensity of drawn yarn A3 is 4.9g/d, and degree of stretching is 29%, and boiling water shrinkage is 13%.

Use polymer P 6, similarly carry out, obtain drawn yarn B4 with drawn yarn B3.The intensity of drawn yarn B4 is 4.6g/d, and degree of stretching is 29%, and boiling water shrinkage is 35%.

Drawn yarn A3 and drawn yarn B3 are mixed fine with air nozzle, similarly carry out, obtain fabric MF3 with the fabric MF1 of embodiment 3.Each is all good for the flexibility of fabric MF3, bulkiness, feel.Similarly, with the fabric MF4 that the combined yarn of drawn yarn B4 and drawn yarn A3 is made, each is all good for its flexibility, bulkiness, feel.

Embodiment 5

With molecular weight is 0.1 part of mixing of antioxidant Irganox1010 of 98 parts of 3 parts of polyethylene glycol (PEG), L-lactides with hydroxyl of 8000 two ends, tin octoate 100ppm, Ciba-Geigy company, in nitrogen atmosphere, stir polymerization 12 minutes with the double screw extruder fusion down at 188 ℃, after the cooling section, in 140 ℃ nitrogen atmosphere, handle 4 hours (solid phase), obtain the block copolymer P1 of PLA and PEG.The molecular weight of polymer P 1 is that the content of 15.5 ten thousand, PEG compositions is about 3%, and fusing point is 175 ℃, and fully the fusion of the fiber of oriented crystalline caloric receptivity is 55J/g.Screw extruder fusion with 230 ℃ of polymer P 1 usefulness, spin from 225 ℃, the spinneret orifice of diameter 0.2mm, in air, cool off, while the speed coiling that oils and divide with 1500m/, under 80 ℃, be stretched to 4.5 times, under 110 ℃ of tensionings, heat-treat, obtain the drawn yarn A1 of 40 dawn/12 threads.The intensity of drawn yarn A1 is 4.5g/d, and degree of stretching is 29%, and boiling water shrinkage is 12%.

(molecular weight is 12.5 ten thousand with 4/1 (mol ratio) random copolymer of poly butylene succinate (PBS) and poly adipate succinic acid ester (PBA), fusing point is 92 ℃, fusion caloric receptivity is 57J/g) 30 parts, 71 parts of L-lactides, 1,010 0.1 parts of above-mentioned Irganox, tin octoate 100ppm mix, below similarly carry out with polymer P 1, obtain block copolymer B P1.The molecular weight of BP1 is 14.7 ten thousand, and 2 main fusing points are respectively 166 ℃ and 85 ℃, and its caloric receptivity can be inferred corresponding with the crystalline phase of poly (l-lactic acid) segment (block) and PBS/PBA copolymer segment respectively for 32J/g and 12J/g.

With the screw extruder fusion of copolymer BP1 with 220 ℃, spin from 225 ℃, the spinneret orifice of diameter 0.2mm, in air, cool off, while the speed coiling that oils and divide with 1500m/, under 80 ℃, be stretched to 4.5 times, do not heat-treat, obtain the drawn yarn B5 of 40 dawn/12 threads.The intensity of drawn yarn B5 is 4.3g/d, and degree of stretching is 35%, and boiling water shrinkage is 36%.

Use each 1 of drawn yarn A1 and drawn yarn B5, mix, obtain to make the two mixed uniformly combined yarn MY3 in the silk cross section with air nozzle.With combined yarn MY3 with the twist yarn of 600 times/m twisting as warp thread, with twisting count is that the twist yarn of 30 times/m is as weft yarn, make 2/1 drillipg, under lax state, in containing 98 ℃ of water of refining agent, handled 15 minutes, and carried out processing (decrement processing) in 10 minutes with 60 ℃ sodium carbonate 2.5% aqueous solution again.Then, washing adds 0.2% soft finishing agent, heat-treats under 120 ℃ of tensionings, obtains fabric MF5.

In order to compare, use 2 drawn yarn A1 and the silk twisted with the fingers, below similarly carry out with MF5, obtain fabric MF6.The characteristic of fabric MF5 and fabric MF6 is shown in Table 2.

Table 2

Fabric	Flexibility	Bulkiness	Feel	Remarks
					MF5	Well	Well	Well	The present invention
MF6	Bad slightly	Bad slightly	Bad	Comparative example

Embodiment 6

With 10 parts of 30 parts of PBS/PBA copolymer pellets, copolymer BP1 (being used to the improve affinity) particles of embodiment 5 and 70 parts of mixing of particle of polymer P 1, with double screw extruder 225 ℃ of following melting mixing, spinning head spinning with 225 ℃, below similarly carry out with the drawn yarn B5 of embodiment 5, obtain drawn yarn B6.The intensity of drawn yarn B6 is 4.3g/d, and degree of stretching is 33%, and boiling water shrinkage is 33%, and fusing point and fusion caloric receptivity is respectively 172 ℃, 31J/g, 88 ℃, 17J/g.Use drawn yarn A1 and 1 drawn yarn B6 of 1 embodiment 5, similarly carry out, obtain combined yarn MY4 with the combined yarn MY3 of embodiment 5.Use combined yarn MY4, similarly carry out, obtain fabric MF7 with the fabric MF5 of embodiment 5.The MF5 of the flexibility of fabric MF7, bulkiness, feel etc. and embodiment 5 is much better than comparative example MF6 about equally, fully confirms to mix fine effect.

Embodiment 7

With molecular weight is 0.1 part of mixing of antioxidant Irganox1010 of polyethylene glycol (PEG) 3 part, the L-lactide 98 part of 8000, two ends with hydroxyl, tin octoate 100ppm, Ciba-Geigy company, in nitrogen atmosphere, stir polymerization 12 minutes with the double screw extruder fusion down at 188 ℃, after the cooling section, in 140 ℃ nitrogen atmosphere, handle 4 hours (solid phase), obtain the block copolymer P1 of PLA and PEG.The molecular weight of polymer P 1 is that the content of 15.5 ten thousand, PEG compositions is about 3%, and fusing point is 175 ℃, and fully the fusion of the fiber of oriented crystalline caloric receptivity is 55J/g.

0.1 part of 71 parts of 30 parts of poly butylene succinates (PBS), L-lactides, above-mentioned Irganox, the tin octoate 100ppm of molecular weight 12.5 ten thousand, 114 ℃ of fusing points, fusion caloric receptivity 68J/g are mixed, below with polymer P 1 polymerization similarly, obtain block copolymer B P2.The molecular weight of BP2 is 13.7 ten thousand, and 2 main fusing points are respectively 165 ℃ and 103 ℃, and its caloric receptivity is inferred corresponding with the crystalline phase of poly (l-lactic acid) segment (block) and PBS segment respectively for 28J/g and 27J/g.

Polymer P 1 is used 220 ℃ screw extruder fusion respectively with copolymer BP2, measure with gear pump on one side, feed compound spinning head on one side, ratio with compound ratio 1/1 (volume ratio) is combined into parallel type shown in Figure 1 with the two, spin from 225 ℃, the spinneret orifice of diameter 0.2mm, in air, cool off, while the speed of dividing with 1500m/ that oils is reeled, 70 ℃ with 4.1 times of stretchings, obtain the drawn yarn Y1 of 150 dawn/48 threads.The intensity of drawn yarn Y1 is the 4.1g/ dawn, and degree of stretching is 27%, and the crimp extension rate when occurring curling in 100 ℃ water is 231%, and is good.

In order to compare, with polymer P 1 fusion, spin from 225 ℃, the spinneret orifice of diameter 0.2mm individually, below similarly carry out with drawn yarn Y1, obtain drawn yarn R1.Similarly carry out, obtain the drawn yarn R2 that makes with copolymer BP2.The percent thermal shrinkage of R1 and R2 is respectively 11.4% and 37.4%.

Embodiment 8

The PBS of embodiment 7 and the particle of polymer P 1 are mixed with 2/3 (weight ratio), screw extruder fusion with 220 ℃, by feeding in the compound spinning head after the ケ ニ ッ Network ス type static mixer with 30 elements (sub-prime), be combined into the parallel type shown in Figure 1A with the polymer P 1 of other fusion, below similarly carry out with the drawn yarn Y1 of embodiment 7, obtain drawn yarn Y2.The intensity of drawn yarn Y2 is 4.1g/d, and degree of stretching is 27%, and the crimp extension rate when occurring curling in 100 ℃ water is 202%, and is good.In order to compare, by the drawn yarn R3 that the mixed polymer of above-mentioned PBS and P1 is made, its shrinkage factor is 29.6%, and the fusing point of measuring with dsc analysis is 174 ℃ and 110 ℃, and the fusion caloric receptivity is respectively 26.3J/g and 25.5J/g.

Embodiment 9

Carry out similarly to Example 7, obtain poly (l-lactic acid) and the block copolymer P1 of PEG and the block copolymer B P2 of poly (l-lactic acid) and poly butylene succinate (PBS).

Polymer P 1 and copolymer BP2 are used 220 ℃ screw extruder fusion respectively,, feed compound spinning head on one side on one side with the gear pump metering, with polymer B P2 as epidermis, polymer P 1 as the core silk, is combined into round with one heart shown in Fig. 4 A with the ratio of compound ratio 2/1 (volume ratio), spins from 225 ℃, the spinneret orifice of diameter 0.2mm, in air, cool off, while the speed coiling that oils and divide with 1500m/, doubling forms tow, under 70 ℃,, obtain tow T1 with 3.9 times of stretchings.Filament number was 3 dawn.

Polymer P 1 220 ℃ of following fusions, is spun from 225 ℃, the spinneret orifice of diameter 0.2mm separately, below similarly carry out, but making draft temperature is 80 ℃, obtains tow T2 with tow T1.With tow T1 and T2 mixed with 1/3 (weight ratio), adopt indentation method that it is curled, it is long that it is cut into 50mm, obtains to mix staple fibre BS1.Use and mix staple fibre BS1, adopting combing method to obtain weight per unit area is 200g/m ²Nonwoven fabric W1.5 nonwoven fabric W1 are piled up, and compacting was handled 15 minutes in 130 ℃ drying machine, obtained by the nonwoven fabric SW1 of heat bonding.Mutually together, be highly suitable for padded coaming between the fiber of nonwoven fabric SW1 by strong binding.Should illustrate that nonwoven fabric W1 can be bonding voluntarily in the wide region of 90～160 ℃ of heat treatment temperatures, certainly, temperature is high more, and is bonding strong more.

In order to compare, as epidermis, as the core silk, carry out compoundly polymer P 1 above-mentioned PBS, below similarly carry out composite spinning with tow T1, the fiber of being reeled can not debatching because PBS is deadlocked.

Embodiment 10

With the particle of the PBS of embodiment 9 and polymer P 1 mixed with 2/3 (weight ratio), screw extruder fusion with 220 ℃, by feeding in the compound spinning head after the ケ ニ ッ Network ス type static mixer that 30 elements are arranged, with the polymer P 1 of other fusion as the core silk, with above-mentioned mixed polymer as epidermis, ratio with compound ratio 1/2 (volume ratio) is combined into concentric core-sheath, below similarly carries out with the nonwoven fabric SW1 of embodiment 9, obtains bonded nonwoven fabric SW2.Mutually together, be highly suitable for padded coaming between the fiber of SW2 by strong binding.Should illustrate that the fusing point of above-mentioned mixed polymer is respectively 173 ℃ and 111 ℃, the fusion caloric receptivity is respectively 33J/g and 21J/g, infers almost not produce the block polymer that generates because of reacting to each other.Long (for example more than 15 minutes in the melting mixing time, particularly more than 20 minutes) occasion under, even some or considerable part form copolymer, but can confirm to keep crystallinity respectively, under the occasion that the fusing point of measuring with DSC separates, can be used for the present invention.

Embodiment 11

With molecular weight is 1,010 0.05 parts of mixing of antioxidant Irganox of polyethylene glycol (PEG) 3 part, the L-lactide 98 part of 8000, two ends with hydroxyl, tin octoate 100ppm, Ciba-Geigy company, in nitrogen atmosphere under 188 ℃, polymerization 15 minutes is stirred in fusion in double screw extruder, after extruding and cool off section by spinning head, in 140 ℃ nitrogen atmosphere, handled (solid phase) 4 hours, with the acetone washing that contains 0.1% hydrochloric acid, then with acetone washing 5 times, dry then, the block copolymer P1 of acquisition PLA and PEG.The molecular weight 14.8 ten thousand of polymer P 1, the content of PEG composition is about 3%, fusing point is 174 ℃, fully the fusion caloric receptivity during oriented crystalline is 5J/g, fusing point and crystallinity etc. are roughly the same with the PLA homopolymers, and melt fluidity and draftability are good, carry out melt composite spinning easily, the boiling water shrinkage of drawn yarn is about 10～15% under most occasions.

(two ends are hydroxyl with the random copolymer of the mol ratio 4/1 of poly butylene succinate and poly adipate succinic acid ester, molecular weight is 12.5 ten thousand, fusing point is 93 ℃) 25 parts, 76 parts of L-lactides, tin octoate 80ppm mix, below similarly carry out polymerization with above-mentioned polymer P 1, obtain about 3/1 block copolymer B P3 of PLA and poly butylene succinate/poly adipate succinic acid ester.The molecular weight of polymer B P3 is 11.7 ten thousand, the fusion endothermic peak that DSC measures has 2 places, its fusing point and fusion caloric receptivity are respectively 168 ℃ (36J/g), 86 ℃ (6.5J/g), think corresponding with polylactic acid chain segment and poly butylene succinate/poly adipate succinic acid ester copolymer segment respectively, the fusing point of this polymer (typical value) is got 168 ℃.By the drawn yarn that polymer B P3 obtains, be about 30～70% under the most occasions of its boiling water shrinkage.

1/50 mole of octanol and tin octoate 100ppm are mixed in 1 mole of the L-lactide, below similarly carry out polymerization, obtain molecular weight that an end has hydroxyl and be 6700 PLA with polymer P 1.Equimolar two isocyanic acid hexylene glycol esters are mixed with the PLA of 180 ℃ of following fusions, make its reaction, have in the prepolymer of isocyanate group to obtaining end, be mixed into molecular weight that an equimolar end has hydroxyl and be 5500 poly dimethyl silane, double screw extruder melting mixing with 180 ℃, make it by having the static mixer of 120 elements on one side then, make its reaction 30 minutes on one side, obtain the block copolymer B P4 of PLA/poly dimethyl silane=about 55/45 (weight ratio).

On one side with polymer B P3 in 220 ℃ of following fusions and feeding, on one side to the polymer B P43% that wherein is mixed into 220 ℃ of following fusions, further mix with the ケ ニ ッ Network ス type static mixer of 60 elements, feed in the compound spinning head with measuring pump then.On the other hand, with polymer P 1 usefulness screw extruder 220 ℃ of following fusions, feed compound spinning head with measuring pump, with polymer P 1 as the composition 7 shown in Fig. 3 B, with the mixture of polymer B P3 and polymer B P4 as the composition 8 shown in Fig. 3 B, be combined into the radial pattern structure shown in Fig. 3 B with compound ratio 4/1 (volume ratio), spin from the spinneret orifice of diameter 0.20mm, in air, cool off, while the speed coiling that oils and divide with 1500m/, under 80 ℃, be stretched to 3.9 times, then under 100 ℃, carry out nervous heat treatment, obtain the stretching D1 of 75 dawn/25 threads.

In order to compare, use polymer P 1 and polymer B P3 (not using the block copolymer B P4 that contains dimethyl silicone polymer), similarly carry out with drawn yarn D1, obtain the stretching D2 (comparative example) of composite fibre.

Make circular knit with drawn yarn D1, it is dropped into to boil in boiling water take out after 15 minutes, after the drying, it contact with the rotary drum that teases sand paper, acquisition napping volume thing K1.Use the pile fiber major part among the volume thing K1 that fiber of the present invention makes to be cut apart, compile thing and have extremely soft sense of touch.Similarly, the volume thing that will be made by the drawn yarn D2 of comparative example boils, dry, napping, and the pile fiber that institute's napping that obtains is compiled among the thing K2 almost can not be cut apart, and the sense of touch of volume thing K2 is hard.

Embodiment 12

Similarly carry out with the manufacturing of polymer B P3 among the embodiment 11, but make that 76 parts of L-lactides and terminal molecular weight with hydroxyl are 12.8 ten thousand, fusing point is 25 parts of reactions of polycaprolactone of 60 ℃, obtains the block copolymer B P5 of polylactic acid and caprolactone=about 3/1 (weight ratio).The molecular weight of polymer B P5 is 10.3 ten thousand, fusing point that DSC measures and fusion caloric receptivity are respectively 166 ℃ (35J/g), 52 (6.6J/g), fusing point (typical value) is 166 ℃, with the drawn yarn that this polymer is made, is about 30～70% under the most occasions of its boiling water shrinkage.

Similarly carry out with the composite fibre D1 of embodiment 11, but replace polymer B P3, obtain composite fibre D3 with above-mentioned polymer B P5.Use composite fibre D3, carry out similarly to Example 11, obtain napping and compile thing K3.Napping of the present invention is compiled thing K3 and is made of the divided fine fibre of pile, has extremely soft sense of touch.

Embodiment 13

With molecular weight 8000, two ends have 98 parts of 3 parts of polyethylene glycol (PEG), L-lactides, the tin octoate 100ppm of hydroxyl, 0.05 part of mixing of antioxidant Irganox1010 of Ciba-Geigy company, in nitrogen atmosphere 188 times in double screw extruder fusion stirred polymerization 15 minutes, extrude from spinning head, after the cooling section, in 140 ℃ nitrogen atmosphere, handled (solid phase) 4 hours, with the acetone washing that contains 0.1% hydrochloric acid, dry after then washing 5 times with acetone, the block copolymer P1 of acquisition PLA and PEG.

(two terminally are hydroxyl to use the random copolymer of the mol ratio 4/1 of poly butylene succinate (PBS) and poly adipate succinic acid ester (PBA), molecular weight is 12.5 ten thousand, fusing point is 93 ℃) 10 parts, 91 parts of L-lactides, tin octoate 90ppm, similarly carry out with the manufacturing of polymer P 1, obtain the block copolymer B P6 of about 9/1 (weight ratio) of PLA and PBS/PBA copolymer.The molecular weight of polymer B P6 is that fusing point and the fusion endothermic peak that 13.5 ten thousand, DSC measure is 174 ℃ and 45J/g, and PLA is modification slightly only, but with the affinity of PBS/PBA copolymer sizable improvement is arranged.By the drawn yarn that 2/1 (weight ratio) mixture of polymer B P6 and above-mentioned PBS/PBA copolymer obtains, its boiling water shrinkage is generally about 30～70%.

Carry out similarly to Example 11, obtain the block copolymer B P4 of PLA/dimethyl silicone polymer=about 55/45 (weight ratio).

The particle of polymer B P2 and above-mentioned PBS/PBA copolymer is mixed with 2/1 (weight ratio), one side also feeds with 220 ℃ screw extruder fusion, on one side to the polymer B P43% that wherein is mixed into 220 ℃ of fusions, ケ ニ ッ Network ス type static mixer with 60 elements further mixes again, feeds in the compound spinning head with measuring pump then.On the other hand, with polymer P 1 usefulness screw extruder 220 ℃ of following fusions, feed compound spinning head with measuring pump, with polymer P 1 as the composition 7 shown in Fig. 3 B, with polymer B P6, the mixture that PBS/PBA copolymer and polymer B P4 constitute is as the composition 8 shown in Fig. 3 B, be combined into the radial pattern structure shown in Fig. 3 B with compound ratio 4/1 (volume ratio), spin from the spinneret orifice of diameter 0.20mm, in air, cool off, while the speed coiling that oils and divide with 1500m/, under 80 ℃, be stretched to 3.9 times, then under 100 ℃ of tensionings, heat-treat, obtain the drawn yarn D4 of 75 dawn/25 threads.In order to compare, except not using silicon-containing polymer BP4, similarly carry out, obtain drawn yarn D5 (comparative example).

Make circular knit with drawn yarn D4, it is dropped into to boil in boiling water take out after 15 minutes, after the drying, it contact with the rotary drum that teases sand paper, acquisition napping volume thing K4.Use the pile fiber major part among the volume thing K4 that fiber of the present invention makes to be cut apart, compile thing and have extremely soft sense of touch.Similarly, the volume thing that will be made by the drawn yarn D5 of comparative example boils, dry, napping, and the pile fiber that institute's napping that obtains is compiled among the thing K2 almost can not be cut apart, and the sense of touch of volume thing K5 is hard.

Embodiment 14

Carry out similarly to Example 13, make end have 10 parts of the polycaprolactones (PCL) and 91 parts of reactions of L-lactide of 60 ℃ of molecular weight 12.8 ten thousand, the fusing points of hydroxyl, obtain the block copolymer B P7 of PLA/PCL=about 9/1 (weight ratio).The molecular weight of polymer B P7 is that fusing point and the fusion caloric receptivity that 11.2 ten thousand, DSC measure is 169 ℃ and 45J/g.With the drawn yarn that the mixture of polymer B P7 and above-mentioned PCL 3/1 (weight ratio) is made, be about 30～50% under the most occasions of its boiling water shrinkage.

Except replace polymer B P6 with polymer B P7, similarly carry out with the manufacturing of the composite fibre D4 of embodiment 13, obtain composite fibre D6.Use composite fibre D6, carry out similarly to Example 13, obtain napping and compile thing K6.Napping of the present invention is compiled thing K6 and is made of the divided fine fibre of pile, has extremely soft sense of touch.

Embodiment 15

Two ends of molecular weight 8000 had 98 parts of 3 parts of polyethylene glycol (PEG), L-lactides, the tin octoate 100ppm of hydroxyl, 0.1 part of mixing of antioxidant Irganox1010 of Ciba-Geigy company, in nitrogen atmosphere under 188 ℃ in double screw extruder fusion stirred polymerization 15 minutes, extrude from spinning head, after the cooling section, in 140 nitrogen atmosphere, handled (solid phase) 4 hours, with the acetone washing that contains 0.1% hydrochloric acid, then with acetone washing 5 times, dry then, the block copolymer P1 of acquisition PLA and PEG.The molecular weight of polymer P 1 is that the content of 15.1 ten thousand, PEG compositions is about 3%, and fusing point is 174 ℃, and fully the fusion caloric receptivity during oriented crystalline is 55J/g.

With 2, (molecular weight is 12.7 ten thousand to the condensation polyester of 2-dimethyl propylene glycol and decanedioic acid, two terminal are hydroxyl) (molecular weight is 12.2 ten thousand for the condensation polyester of 15 parts, butanediol and adipic acid, two ends are hydroxyl) 15 parts, 71 parts of L-lactides, tin octoate 80ppm mix, below similarly carry out with polymer P 1, obtain polymer B P8.Polymer B P8 is as rigid chain segment with crystalline polylactic acid, to gather the block copolymer of the mixture of decanedioic acid dimethyl propylene diol ester (PDMPS) and poly adipate succinic acid ester (PBA) as soft segment, fusing point is 164 ℃, recepts the caloric to be that 25.5J/g, molecular weight are 11.9 ten thousand.The ratio of the rigid chain segment composition (PLA) of polymer B P8 is about 70%, from fusing point and caloric receptivity etc., infers that crystalline portion is about 50%.Should illustrate that the molecular weight ratio soft segment of polymer B P8 is low with the PDMPS or the PBA of raw material, think that this is because ester exchange reaction or decomposition have taken place its part.But gpc analysis demonstrates, and the main distribution of molecular weight is a peak, confirms to generate the even block copolymer of PLA/PDMPS/PBA.See that from dsc analysis the endothermic peak relevant with soft segment at 35 ℃ with below 80 ℃ of 2J/g of this 2 place, can be ignored, in fact soft segment is counted as noncrystalline.Should illustrate that glass transition temperature is about-12 ℃.

Polymer P 1 and polymer B P8 are used 220 ℃ screw extruder fusion respectively, feed 2 polymer supply units of compound spinning head.Two kinds of polymer are combined into the parallel type structure shown in Figure 1A (compound ratio 1/1), spin from diameter 0.22mm, 225 ℃ spinneret orifice, in air, cool off, while the speed of dividing with 4000m/ that oils is reeled, stretch 1.5 times down at 80 ℃, obtain the drawn yarn FS1 of 70 dawn/24 threads.The intensity of drawn yarn FS1 is 4.7g/d, and degree of stretching is 29%, and the crimp extension rate after occurring curling is 330%, and is good.

For ease of reference, similarly carry out with the manufacturing of polymer B P8, make as 30 parts of the poly butylene succinates (114 ℃ of fusing points) of the molecular weight 12.5 ten thousand of soft segment composition and L-lactide and react for 70 parts, make molecular weight and be PLA/PBS block copolymer B P9 of 11.8 ten thousand as the rigid chain segment composition.The dsc analysis of polymer B P9 shows 2 crystalline melt points, and its fusing point and fusion caloric receptivity is respectively 103 ℃, 27J/g, 166 ℃, 29J/g.Similarly carry out with drawn yarn FS1, make drawn yarn FS2 with polymer B P9 with polymer P 1.The intensity of drawn yarn FS2 is 4.7g/d, and degree of stretching is 28%, and the crimp extension rate after occurring curling is 121%, demonstrate quite good crimpiness, but crimpiness is poorer than drawn yarn FS1.

Embodiment 16

Polydiethylene glycol sebacate is mixed with 30 parts of 1/1 (mol ratio) random copolymers, 71 parts of L-lactides, the tin octoate 80ppm of poly-decanedioic acid dimethyl propylene diol ester, below similarly carry out, obtain block copolymer B P10 with the polymer B P8 of embodiment 15.The crystalline melt point of polymer B P10 is 164 ℃, recepts the caloric to be 25J/g, has only 1 endothermic peak, and soft segment is non-crystalline.

On the other hand, two terminal 1 mole of poly-adipic acid dimethyl propylene diol ester that have hydroxyl for 1 mole of two end of polyethylene glycol adipate of hydroxyl with molecular weight 12000 with molecular weight 8000, in stream of nitrogen gas, under 100 ℃, fusion is on one side stirred, slowly splash into 4.5 moles of two isocyanic acid benzhydryl esters on one side, make its reaction 3 hours, obtain prepolymer, in this prepolymer total amount, add 1 on one side, 2.5 moles of 4-butanediols are in 200 ℃ the twin-screw mixer extruder Yi Bian feed temperature continuously, make its reaction 7 minutes, be expressed into the water from spinning head then, granulation, drying obtains polymer B P11.Polymer B P11 is made of the rigid chain segment with urethane bond and non-crystalline soft segment, and fusing point is 193 ℃, and molecular weight is 49000.

Use polymer P 1 and the polymer B P10 of embodiment 15, below similarly carry out, obtain drawn yarn FS3 with the drawn yarn FS1 of embodiment 15.The intensity of drawn yarn FS3 is 4.7g/d, and degree of stretching is 31%, and the crimp extension rate is 323%, and crimpiness is good.

Similarly, use polymer P 1 and the polymer B P11 of embodiment 15, below similarly carry out, obtain drawn yarn FS4 with the drawn yarn FS1 of embodiment 15.The intensity of drawn yarn FS4 is 4.4g/d, and degree of stretching is 40%, and the crimp extension rate is 453%, and crimpiness is extremely good.

Embodiment 17

With two ends of molecular weight 8000 have 98 parts of 3 parts of polyethylene glycol (PEG), L-lactides, the tin octoate 100ppm of hydroxyl, antioxidant Irganox10100.1 part of Ciba-Geigy company is mixed, in nitrogen atmosphere under 188 ℃, polymerization 12 minutes is stirred in fusion in double screw extruder, after the cooling section, in 140 ℃ nitrogen atmosphere, handled (solid phase) 4 hours, obtain the block copolymer P1 of PLA and PEG.The molecular weight of polymer P 1 is that the content of 15.5 ten thousand, PEG compositions is about 3%, and fusing point is 175 ℃, and fully the fusion of the fiber of oriented crystalline caloric receptivity is 55J/g.Screw extruder fusion with 230 ℃ of polymer P 1 usefulness, spin from 225 ℃, the spinneret orifice of diameter 0.2mm, in air, cool off, while the speed coiling that oils and divide with 1500m/, stretch 4.5 times down at 80 ℃, under 110 ℃, carry out nervous heat treatment, obtain the drawn yarn A1 of 40 dawn/12 threads.The intensity of drawn yarn A1 is 4.9g/d, and degree of stretching is 29%, and boiling water shrinkage is 12%.

Will by butanediol, propylene glycol, succinic acid, adipic acid etc. the mole block copolymer (molecular weight is 8.5 ten thousand, amorphism) 30 parts, 71 parts of L-lactides, 0.1 part of above-mentioned Irganox, tin octoate 100ppm mix, below similarly carry out with polymer P 1, obtain block copolymer B P12.The molecular weight of BP12 is 14.7 ten thousand, and fusing point is 166 ℃, recepts the caloric to be 30J/g, and this is the crystalline melt point of poly (l-lactic acid) segment (block).

With the screw extruder fusion of copolymer BP12 with 220 ℃, spin from 225 ℃, the spinneret orifice of diameter 0.2mm, in air, cool off, while the speed coiling that oils and divide with 1500m/, stretch 4.5 times down at 80 ℃, do not heat-treat, obtain the drawn yarn BS1 of 40 dawn/12 threads.The intensity of drawn yarn BS1 is 4.5g/d, and degree of stretching is 35%, and boiling water shrinkage is 35%.

Use each 1 of drawn yarn A1 and drawn yarn BS1, mix, obtain to make the two mixed uniformly combined yarn MYS1 in the silk cross section with air nozzle.With combined yarn MYS1 with the twist yarn of 600 times/m twisting as warp thread, with twisting count is that the twist yarn of 30 times/m is as weft yarn, make 2/1 drillipg, after the refining under relaxed state, 120 ℃ of xeothermic down heat treatments 14 minutes, carry out processing (decrement processing) in 10 minutes with 80 ℃ sodium carbonate 2.5% aqueous solution again.Washing adds 0.2% soft finishing agent then, carries out nervous heat treatment under 135 ℃, obtains fabric MFS1.

In order to compare, use 2 and the twisted filaments of drawn yarn A1, below similarly carry out with MFS1, obtain fabric MF6.The characteristic of fabric MFS1 and fabric MF6 is shown in Table 3.

Table 3

Fabric	Flexibility	Bulkiness	Feel	Remarks
					MFS1	Well	Well	Well	The present invention
MF6	Bad slightly	Bad slightly	Bad	Comparative example

Embodiment 18

(molecular weight is 12.5 ten thousand two ends to be had 4/1 (mol ratio) random copolymer of poly butylene succinate/poly adipate succinic acid ester of hydroxyl, fusing point is 92 ℃) 14 parts, poly-(adipic acid 2,2-dimethyl propylene diol ester) (fusing point is 37 ℃ to homopolymers, molecular weight is 8.1 ten thousand, two ends are hydroxyl) 14 parts, 73 parts of L-lactides, 0.1 part of mixing of tin octoate 100ppm, Irganox, below react similarly to Example 17, obtain block copolymer B P13.The molecular weight of polymer B P13 is 14.7 ten thousand, and fusing point is 168 ℃, and this is the fusing point of polylactic acid chain segment.

Make polymer B P13 220 ℃ of following fusions,, carry out similarly to Example 17, obtain drawn yarn BS2 with 225 ℃ spinning head spinning.The intensity of drawn yarn BS2 is 4.6g/d, and degree of stretching is 33%, and boiling water shrinkage is 36%.Drawn yarn A1 and 1 drawn yarn BS2 with 1 embodiment 17 carry out similarly to Example 17, obtain combined yarn MYS2, use combined yarn MYS2, carry out similarly to Example 17, obtain combined yarn fabric MFS2.The flexibility of fabric MFS2, bulkiness, feel etc. are roughly the same with the MFS1 of embodiment 17, are much better than comparative example MF6, fully confirm to mix fine effect.

Embodiment 19

The ethylene glycol that will be equivalent to L-lactide 0.05%, 0.1% Irganox, the tin octoate of 100ppm mix with the L-lactide, below react similarly to Example 17, obtain molecular weight that two ends have hydroxyl and be 5.2 ten thousand PLA PL1.The molecular weight that two ends are had a hydroxyl is that molecular weight that 1 mole, two ends of polyethylene glycol adipate of 12000 have hydroxyl is 1 mole of mixing of poly-adipic acid dimethyl propylene diol ester of 8000, in 100 ℃ stream of nitrogen gas, fusion is on one side stirred, slowly splash into 4.02 moles of two isocyanic acid benzene methyls on one side, reacted 3 hours, and obtained prepolymer PP1.Use double screw extruder, 185 ℃ following fusions stir above-mentioned PLA 1 part on one side, on one side to wherein being mixed into 0.4 part of prepolymer PP1, laruyl alcohol 2%, reacting and extrude from spinning head after 5 minutes, in water, cool off, cut off, obtain block copolymer B P14.Block copolymer B P14 is made of rigid chain segment with PLA crystallization and urethane bond and amorphism aliphatic polyester segment, and the fusing point of rigid chain segment is 172 ℃, and molecular weight is 18.8 ten thousand.With the screw extruder fusion of BP14 with 220 ℃, spin from 230 ℃, 12 spinneret orifices of diameter 0.2mm, polymer P 1 fiber doubling with the embodiment 17 of same melt spinning, carrying out air on one side mixes fine, the speed of dividing with 1500m/ is reeled on one side, under 80 ℃, be stretched to 3.9 times, obtain the combined yarn MYS3 of 80 dawn/24 threads.Use MYS3, make fabric similarly to Example 17, obtain to have the bulkiness same good, the fabric MFS3 of flexibility with MFS1.

Embodiment 20

With molecular weight is 8000, two ends are 3 parts of the polyethylene glycol (PEG) of hydroxyl, 98 parts of L-lactides, tin octoate 100ppm, 0.1 part of mixing of the antioxidant Irganox1010 of Ciba-Geigy company, in nitrogen atmosphere under 188 ℃, polymerization 12 minutes is stirred in fusion in double screw extruder, at last, mix 0.1% silicone oil (dimethyl siloxane), extrude from spinning head then, after the cooling section, in 140 ℃ nitrogen atmosphere, handled (solid phase) 4 hours, with the acetone washing that contains 0.1% hydrochloric acid, then, dry then with acetone washing 5 times, the block copolymer P1 of acquisition PLA (PLA) and PEG.The molecular weight of polymer P 1 is that the content of 12.2 ten thousand, PEG compositions is about 3%, and fusing point is 174 ℃, and fully the fusion caloric receptivity during oriented crystalline is 55J/g.

(two ends are hydroxyl with the random copolymer of the mol ratio 4/1 of poly butylene succinate (PBS) and poly adipate succinic acid ester (PBA), molecular weight is 12.5 ten thousand, fusing point is 93 ℃) 80 parts, molecular weight is 5 parts of 20000 PEG, 20 parts of L-lactides, tin octoate 30ppm, 0.1 part of mixing of above-mentioned Irganox, below similarly carry out polymerization with above-mentioned polymer P 1, acquisition is by the block copolymer (PBS/PBA/PLA) of PBS/PBA copolymer and PLA and the mixture M P1 of block copolymer (PLA/PEG) formation of PLA and polyethylene glycol, and its fusing point is 90 ℃.The reactivity of supposing each terminal hydroxyl equates, the lactide total overall reaction, infer that the PLA composition in the PBS/PBA/PLA block copolymer is about 18%, molecular weight is about about 150,000, PLA composition in the PLA/PEG block copolymer is about 52%, and molecular weight is about 40,000, and two kinds of polymer are owing to have this common component of PLA, affinity is quite high, can mix equably.

With 20 parts of L-lactides, 0.2 part of above-mentioned Irganox, tin octoate 20ppm and molecular weight is that 20000 PEG mixes for 80 parts, makes its reaction 30 minutes under 180 ℃, obtains molecular weight and be 40,000 PEG/PLA block copolymer.With 50 parts of 50 parts of PEG, the neopelexes of molecular weight 20000,0.3 part of mixing of above-mentioned Irganox, under 1 holder of 180 ℃, pressure, stirred 1 hour, it is dewatered fully, 4 parts of 1 part of this dehydrate and the institute PEG/PLA block copolymers that obtains 180 ℃ of following melting mixing, are obtained mixture M P2.Again with MP2 and above-mentioned MP1 with 7/93 weight ratio 220 ℃ of following melting mixing, obtain mixture M P3.

With PLA/PEG block copolymer P1 and mixture M P3 respectively 220 ℃ of following fusions, measure with gear pump respectively on one side, feed compound spinning head on one side, with P1 as the composition 7 shown in Fig. 3 B, with MP3 as the composition 8 shown in Fig. 3 B, be combined into the radial structure shown in Fig. 3 B with compound ratio than (volume ratio) 4/1, from 220 ℃, the spinneret orifice of diameter 0.25mm spins, in air, cool off, while the speed coiling that oils and divide with 1500m/, stretch 3.9 times down at 80 ℃, then under 100 ℃, carry out nervous heat treatment, obtain the drawn yarn DF 1 of 75 dawn/25 threads.In order to compare, similarly carry out with above-mentioned, P1 as the composition 7 shown in Fig. 3 B, as the composition 8 shown in Fig. 3 B, is obtained drawn yarn DF2 (comparative example) with the poly butylene succinate of 116 ℃ of fusing points, molecular weight 12.5 ten thousand.

Make circular knit with drawn yarn DF1, handle after 10 minutes in sodium carbonate 3% aqueous solution with 98 ℃ of its inputs and take out, after the drying, it is contacted with the rotary drum that teases sand paper, obtain napping and compile thing DK1.Among the volume thing DK1 that makes with fiber of the present invention, the pile fiber major part is cut apart, and compiles thing and has extremely soft sense of touch.Similarly, the volume thing that will be made by the drawn yarn DF2 of comparative example boils, dry, napping, and the pile fiber that institute's napping that obtains is compiled among the thing DK2 almost can not be cut apart, and the sense of touch of volume thing DK2 is hard.

Embodiment 21

Replace PBS/PBA random copolymer (fusing point is 93 ℃) with poly butylene succinate (homopolymers) (fusing point is 116 ℃, and molecular weight is 12.5 ten thousand), in addition, carry out similarly to Example 20, obtain drawn yarn DF3, similarly carry out, obtain napping and compile thing DK3 with it.Thing DK3 is compiled in napping and napping volume thing DK1 is same, and pile is cut apart fully, and flexibility is good.

Embodiment 22

With molecular weight is 8000, two terminal 0.1 part of mixing of antioxidant Irganox1010 for 4 parts of the polyethylene glycol of hydroxyl (PEG), 97 parts of L-lactides, tin octoate 100ppm, Ciba-Geigy company, in nitrogen atmosphere under 188 ℃, polymerization 12 minutes is stirred in fusion in double screw extruder, after the cooling section, in 140 ℃ nitrogen atmosphere, handled (solid phase) 4 hours, obtain the block copolymer P1a of PLA and PEG.The molecular weight of polymer P 1a is that the content of 16.2 ten thousand, PEG compositions is about 4%, and fusing point is 175 ℃, and fully the fusion caloric receptivity during oriented crystalline is 55J/g.

(molecular weight is 12.5 ten thousand with 4/1 (mol ratio) random copolymer of poly butylene succinate (PBS) and poly adipate succinic acid ester (PBA), fusing point is 92 ℃, fusion caloric receptivity is 57J/g) 30 parts, 71 parts of L-lactides, 0.1 part of above-mentioned Irganox, tin octoate 100ppm mix, with above-mentioned polymerization, the acquisition block copolymer B P1 of similarly carrying out.The molecular weight of BP1 is 13.7 ten thousand, and 2 main fusing points are 165 ℃ and 85 ℃, and its caloric receptivity is inferred corresponding with the crystalline phase of poly (l-lactic acid) segment (block) and PBS/PBA copolymer segment respectively for 32J/g and 12J/g.It is 92 ℃ PBS/PBA copolymer about 30% that BP1 contains fusing point as composition.

Polymer P 1a and polymer B P1 are used 220 ℃ screw extruder fusion respectively, feed in the compound spinning head on one side with the gear pump metering on one side, with polymer P 1a as epidermis, with polymer B P1 as the core silk, be combined into concentric type structure shown in Fig. 5 A with the ratio of compound ratio 1/4 (volume ratio), spin from 225 ℃, the spinneret orifice of diameter 0.2mm, in air, cool off, while the speed coiling that oils and divide with 1500m/, stretch 4.1 times down at 60 ℃, obtain the drawn yarn Z1 of 70 dawn (d)/24 threads (f).The intensity of drawn yarn Z1 is the 4.1g/ dawn, and degree of stretching is that 27%, 100 ℃ of shrinkage factor in the water is 29.3%.

With polymer P 1a fusion, spin separately from 220 ℃, the spinneret orifice of diameter 0.2mm, below similarly carry out, but nervous heat treatment is carried out in the back that stretches under 90 ℃, obtain the drawn yarn Z2 of 70d/24f with drawn yarn Z1.The intensity of drawn yarn Z2 is 4.8g/d, and degree of stretching is that the shrinkage factor of 29%, 100 ℃ of water is 12.6%.

It is fine that drawn yarn Z1 and drawn yarn Z2 are mixed on one side by air nozzle on one side, will be with the twist yarn of 900t/m twisting as warp thread, with twisting count is that the twist yarn of 200t/m is as weft yarn, weave flat fabric, in containing 100 ℃ of water of surfactant (washing agent) 0.1%, shrink process is 15 minutes under no tension force, then, containing the blue 3RT of DISPERSE DYES Miketon polyester (society's system is pressed in Mitsui east) 1% (owf), acetic acid 0.02%, in 100 ℃ of water of bleeding agent (activating agent) 0.2%, dyeed 60 minutes, and after the washing, added soft finishing agent 0.1% again, dry under weak tension force, obtain fabric ZW1.

In order to compare, mix with 2 drawn yarn Z2 fine, after the twisting, below similarly shrink, dyeing, soft finish, drying, obtain fabric ZW2 thus.

Bulkiness, the flexibility of fabric ZW1 and ZW2 are shown in Table 4.As shown in table 4, fabric ZW1 of the present invention has bulkiness and the flexibility better than comparative example ZW2.

Table 4

Fabric	Bulkiness	Flexibility	Remarks
				ZW1	Well	Well	The present invention
ZW2	Bad	Bad	Comparative example

Embodiment 23

The polymer P 1a of embodiment 22 as epidermis, as the core silk, is combined into concentric type structure Fig. 5 A shown in the ratio of compound ratio 1/3 with the PBS/PBA copolymer of embodiment 22, below similarly carries out, obtain drawn yarn Z3 with the drawn yarn Z1 of embodiment 22.The intensity of drawn yarn Z3 is 3.1g/d, and degree of stretching is 33%, and the shrinkage factor in 100 ℃ of water is 27.1%.Mix the drawn yarn Z2 of drawn yarn Z3 and embodiment 22 fine, below similarly carry out twist yarn, braiding, washing and shrink process with the fabric of embodiment 22, under 90 ℃, carry out alkali decrement processing 12 minutes with sodium carbonate 0.3% aqueous solution again, the polymer unwinds of fiber surface is removed about 11%, then wash, dyeing, soft finish, drying, obtain fabric ZW3 thus.

With the particle of the PBS/PBA copolymer of embodiment 22 and polymer P 1a mixed with 1/1 (weight ratio), screw extruder fusion with 220 ℃, behind ケ ニ ッ Network ス type static mixer with 30 elements, feed in the compound spinning head, it as the core silk, as epidermis, is combined into concentric core-sheath structure Fig. 5 A shown in the ratio of compound ratio 1/3 with the polymer P 1a of other fusion, below similarly carry out with the drawn yarn Z1 of embodiment 22, obtain drawn yarn Z4.The intensity of drawn yarn Z4 is 3.4g/d, and degree of stretching is 32%, and the shrinkage factor in 100 ℃ of water is 25.8%.The drawn yarn Z2 of drawn yarn Z4 and embodiment 22 is mixed fine, below similarly carry out, obtain fabric ZW4 with fabric ZW3.The bulkiness of fabric ZW3 and ZW4, flexibility are all good, and the help that this and alkali decrement are processed has much relations.Should illustrate that if they are not carried out the processing of alkali decrement, then feel is identical with the degree of the fabric ZW1 of embodiment 22.

Claims (10)

1. A fiber comprising (A): a fiber component composed of a crystalline aliphatic polyester polymer having a melting point of 140°C or higher, and (B): a combination of component (H) and component (S) Composed of fiber components; wherein, component (H) is a crystalline aliphatic polyester having a melting point of 110°C or higher, and component (S) is a crystal having a melting point of 120°C or lower and 10°C or more lower than the melting point of the above-mentioned polymer (A) Non-crystalline aliphatic polyester or non-crystalline aliphatic polyester with a glass transition temperature below 30°C. 2. The fiber described in claim 1, wherein the fiber component (B) is composed of an aliphatic polyester crystalline segment (H) with a melting point above 140° C. and a melting point below 120° C. and a glass transition temperature of 30° C. It consists of a block copolymer in which non-crystalline aliphatic polyester segments (S) below ℃ are bonded together, and at least one of the polymer (A) and the polymer (B) contains 0.05% by weight or more of organopolysiloxane Components, the fiber component (A) and the fiber component (B) are combined in a single fiber, so that in the fiber cross section, the fiber component (B) divides the fiber component (A) into at least 2 parts, and the two components ( A) and (B) occupy part of the surface of the fiber. 3. The fiber according to claim 1, wherein the fiber component (B) is composed of a crystalline aliphatic polyester (H) with a melting point of 140° C. A polymer composition (B) composed of a mixture of crystalline aliphatic polyesters (S), wherein at least one of the polymer (A) and the polymer composition (B) contains 0.05% by weight or more of an organopolysiloxane component , the fiber component (A) is combined with the fiber component (B) in a single fiber, so that in the fiber cross section, the fiber component (B) divides the fiber component (A) into at least 2 parts, and the two components (A ) and (B) occupy part of the surface of the fiber. 4. The fiber as claimed in claim 1, which is composed of (A): a fiber component made of a crystalline aliphatic polyester polymer having a melting point of 140° C. or higher and a heat of fusion of 20 Joules/gram or higher, and (B ): a fiber component composed of block copolymers and/or mixtures of at least two aliphatic polyesters with a melting point difference of 10°C or more; wherein, (B) is composed of A block containing 95 to 10% by weight of a high melting point component (H) with a melting point of 40 to 120°C and a melting endothermic heat of 3 Joules/g or more with a low melting point component (S) of 5 to 90% by weight Fiber components made from copolymers and/or blends. 5. The fiber according to claim 4, which is a composite yarn formed by mixing molecularly oriented fibers composed of the fiber component (A) and molecularly oriented fibers composed of the fiber component (B). 6. The fiber according to claim 4, wherein the fiber component (B) is a block copolymer and/or a mixture of at least two crystalline aliphatic polyesters having a melting point difference of 20°C or more, and contains a melting point of 130°C 90 to 10% by weight of the high melting point component (H) having a melting endothermic heat of 3 joules/g or more, and 10 to 10% by weight of a low melting point component (S) having a melting point of 40 to 120°C and a melting endothermic heat of 3 joules/g or more 90% by weight of block copolymer and/or mixture, the fiber component (A) and the fiber component (B) are joined concentrically in a single fiber, and the fiber component (B) occupies at least a part of the surface of the fiber to form a composite fiber. 7. The fiber according to claim 4, wherein the fiber component (B) is a block copolymer and/or a mixture of at least two crystalline aliphatic polyesters having a melting point difference of 20° C. 90 to 10% by weight of the above, a high melting point component (H) with a melting endothermic heat of 3 joules/g or more, and 10% of a low melting point component (S) with a melting point of 40 to 120°C and a melting endothermic heat of 3 joules/g or more ~90% by weight of block copolymers and/or mixtures, fiber component (A) and fiber component (B) are eccentrically bonded in a single fiber to form a composite fiber. 8. The fiber described in claim 1, which is a fiber component composed of (A) a crystalline aliphatic polyester polymer having a melting point of 140° C. Composed of a fiber component composed of a block copolymer combining a soft segment (S) and a rigid segment (H); wherein the soft segment (S) is composed of an aliphatic polyester, which is practically non-crystalline Yes, the glass transition temperature is 30°C or lower, and the rigid segment (H) is composed of a crystalline aliphatic polyester having a melting point of 110°C or higher. 9. The fiber according to claim 8, which is a hybrid yarn formed by mixing molecularly oriented fibers composed of the fiber component (A) and molecularly oriented fibers composed of the fiber component (B). 10. The fiber according to claim 8, wherein the fiber component (B) is composed of a block copolymer with a glass transition temperature of the soft segment (S) below 20° C. Composite eccentrically within the fibers.

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